Adhesive composition, adhesive optical film and image display device

ABSTRACT

To provide an adhesive composition which shows high adhesion with a glass substrate and has excellent heat resistance, moisture resistance and moist heat resistance, an adhesive optical film comprising an adhesive layer made of the adhesive composition, which shows high adhesion between the adhesive layer and an optical film and effectively suppresses the occurrence of adhesive residue and lack of adhesive and also has excellent heat resistance, moisture resistance and moist heat resistance, and an image display device comprising the adhesive optical film, the adhesive optical film comprises an optical film  1 , an adhesive layer  3  made of a water dispersible adhesive composition comprising, as raw monomers, an alkyl (meth)acrylate ester whose alkyl group has 4 to 18 carbon atoms, a carboxyl group-containing vinyl monomer, a phosphoric acid group-containing vinyl monomer, and a copolymerizable vinyl monomer which is optionally copolymerizable with the above monomers, wherein a carboxyl group concentration is from 0.05 to 1.50 mmol/g and a phosphoric acid group concentration is from 0.01 to 0.45 mmol/g in the raw monomers, an under coat layer  2  containing an oxazoline group-containing polymer, and being interposed between the optical film  1  and the adhesive layer  3 , and the adhesive optical film is applied onto an image display device.

The present application is a Divisional Application of U.S. patentapplication Ser. No. 11/337,838, filed on Jan. 24, 2006, which claimspriority from Japanese Patent Application No. 2005-018831, filed on Jan.26, 2005, Japanese Patent Application No. 2005-054476, filed on Feb. 28,2005, Japanese Patent Application No. 2005-331825, filed on Nov. 16,2005, Japanese Patent Application No. 2005-340658, filed on Nov. 25,2005, Japanese Patent Application No. 2005-361872, filed on Dec. 15,2005, and Japanese Patent Application No. 2005-361873, filed on Dec. 15,2005, the contents of each and all of which are herein incorporated byreference in their entirety

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an adhesive composition, an adhesiveoptical film, and an image display device. More particularly, it relatesto an adhesive composition, an adhesive optical film used as variousoptical films comprising an adhesive layer and an under coat layer, andan image display device.

2. Description of the Background Art

Heretofore, optical films such as polarizing film, phase differencefilm, luminance improving film, and view-angle expansion film have beenused for various industrial purposes and, for example, these opticalfilms are used for sticking onto image display devices such as liquidcrystal display, organic electroluminescence device (organic EL displaydevice), and plasma display panel (PDP).

As the optical film to be sticked onto a liquid crystal display, anadhesive optical film comprising an optical film laminated with anadhesive is known.

For example, there is proposed an adhesive optical film in which anisocyanate-based polyfunctional compound is added to an acrylic polymersolution to prepare an adhesive solution and layer made of the resultingadhesive solution is laminated on a polarizing film comprising an undercoat layer (anchor layer) made of a water dispersible polyester-basedresin (see, for example, Japanese Unexamined Patent Publication No.2004-54007).

For example, there is also proposed an adhesive optical film in which anadhesive layer is laminated on an optical film with an under coat layermade of a polyamine compound interposed (see, for example, JapaneseUnexamined Patent Publication No. 2004-78143).

Further, for example, there is also proposed an adhesive polarizingplate in which an acrylic adhesive layer is laminated on a polarizingplate with an under coat layer made of a polyacrylic ester having aprimary amino group (see, for example, Japanese Unexamined PatentPublication No. 10-20118).

In view of the environmental burden, it has recently been required toreduce the use of an organic solvent, and a solvent-based adhesivecontaining an organic solvent as a solvent is replaced by a waterdispersible adhesive containing water as a dispersion medium.

As such the water dispersible adhesive, for example, there is proposed apressure sensitive adhesive composition comprising a copolymer emulsionin which a copolymer contains 2-ethylhexyl methacrylate of the amount of10 to 50% by weight based on the entire copolymer and the copolymer hasa glass transition temperature of −25° C. or lower (see, for example,Japanese Unexamined Patent Publication No. 2001-254063).

However, conventional adhesives including those disclosed in theabove-mentioned Japanese Unexamined Patent Publication No. 2004-54007,Japanese Unexamined Patent Publication No. 2004-78143 and JapaneseUnexamined Patent Publication No. 10-20118 show low adhesion with anoptical film. When an optical film is sticked onto a liquid crystaldisplay, the optical film is usually sticked onto the liquid crystaldisplay and, if necessary, the optical film is once removed forpositioning and then sticked again (reworking). However, these adhesivesare remained on the surface of the liquid crystal display when removed(hereinafter referred to as “adhesive residue”), and thus reworkabilityis insufficient.

When the terminal portion of an adhesive optical film contacts withpersons or articles in the vicinity in case of handling in the step ofcutting or conveying the adhesive optical film, the adhesive is removedat the contact portion (hereinafter referred to as “lack of adhesive”).When the adhesive optical film, which caused lack of adhesive, isattached onto a liquid crystal display, a problem such as poor displayoccurs.

Conventional water dispersible adhesives including those disclosed inthe above-mentioned Japanese Unexamined Patent Publication No.2001-254063 show particularly low adhesion to a hydrophilic adherendsuch as glass and therefore it has difficulty to firmly stick to a glasssubstrate of a liquid crystal display, although adhesion to ahydrophobic adherend such as polyolefin is improved.

Furthermore, excellent heat resistance, which does not cause defects dueto severe heating, is required for an adhesive to be laminated for anadhesive optical film. According to the purposes, the adhesive may beused under not only severe heating conditions but also severe heatingand humidifying conditions, and thus excellent moist heat resistance isalso required.

With respect to a water dispersible adhesive to be laminated on anoptical film, heat resistance and moisture resistance, which does notcause deterioration of adhesion due to severe heating and humidifying,are required.

SUMMARY OF THE INVENTION

An object of the present invention is to provide an adhesive compositionwhich shows excellent adhesion with a glass substrate and has excellentheat resistance, moisture resistance or moist heat resistance, anadhesive optical film comprising an adhesive layer made of the adhesivecomposition, which shows excellent adhesion between the adhesive layerand an optical film and effectively suppresses an occurrence of anadhesive residue and a lack of adhesive and also has excellent heatresistance, moisture resistance and moist heat resistance, and an imagedisplay device comprising the adhesive optical film.

The adhesive composition of the present invention comprises, as rawmonomers, an alkyl (meth)acrylate ester whose alkyl group has 4 to 18carbon atoms, a carboxyl group-containing vinyl monomer, a phosphoricacid group-containing vinyl monomer represented by the following generalformula (1), and a copolymerizable vinyl monomer which is optionallycopolymerizable with the above monomers, wherein, with respect to aproportion of the raw monomers, an amount of the alkyl (meth)acrylateester is from 60 to 99 parts by weight based on 100 parts by weight ofthe total amount of the raw monomers, and a total proportion of thecarboxyl group-containing vinyl monomer, the phosphoric acidgroup-containing vinyl monomer and the copolymerizable vinyl monomer isfrom 1 to 40 parts by weight based on 100 parts by weight of the totalamount of the raw monomers, and a carboxyl group concentration is from0.05 to 1.50 mmol/g and a phosphoric acid group concentration is from0.01 to 0.45 mmol/g in the raw monomers:

in the general formula (1), R¹ represents a hydrogen atom or a methylgroup, R² represents a polyoxyalkylene group represented by thefollowing general formula (2), and X represents a phosphoric acid groupor a salt thereof represented by the following general formula (3),

in the general formula (2), n represents an integer of 1 to 4, and mrepresents an integer of 2 or more, and

in the general formula (3), M¹ and M² each independently represents ahydrogen atom or a cation.

Further, in the adhesive composition of the present invention, withrespect to the proportion of the raw monomers, the amount of the alkyl(meth)acrylate ester is preferably from 60 to 99 parts by weight, theamount of carboxyl group-containing vinyl monomer is preferably from 0.5to 15 parts by weight, the amount of the phosphoric acidgroup-containing vinyl monomer is preferably from 0.5 to 20 parts byweight, and the proportion of the copolymerizable vinyl monomer ispreferably 39 parts by weight or less, based on 100 parts by weight ofthe total amount of the raw monomers.

Further, it is preferable that the adhesive composition of the presentinvention contains, as the copolymerizable vinyl monomer, an alkoxysilylgroup-containing vinyl monomer, the amount being from 0.001 to 1 partsby weight based on 100 parts by weight of the total amount of the rawmonomers.

It is preferable that the adhesive composition of the present inventionis a water dispersible adhesive composition.

An adhesive optical film of the present invention includes an adhesivelayer, the adhesive layer being made of an adhesive composition thatincludes, as raw monomers, an alkyl (meth)acrylate ester whose alkylgroup has 4 to 18 carbon atoms, a carboxyl group-containing vinylmonomer, a phosphoric acid group-containing vinyl monomer represented bythe following general formula (1), and a copolymerizable vinyl monomerwhich is optionally copolymerizable with the above monomers, whereinwith respect to a proportion of the raw monomers, an amount of the alkyl(meth) acrylate ester is from 60 to 99 parts by weight based on 100parts by weight of the total amount of the raw monomers, and a totalproportion of the carboxyl group-containing vinyl monomer, thephosphoric acid group-containing vinyl monomer and the copolymerizablevinyl monomer is from 1 to 40 parts by weight based on 100 parts byweight of the total amount of the raw monomers, and a carboxyl groupconcentration is from 0.05 to 1.50 mmol/g and a phosphoric acid groupconcentration is from 0.01 to 0.45 mmol/g in the raw monomers:

in the general formula (1), R¹ represents a hydrogen atom or a methylgroup, R² represents a polyoxyalkylene group represented by thefollowing general formula (2), and X represents a phosphoric acid groupor a salt thereof represented by the following general formula (3)

in the general formula (2), n represents an integer of 1 to 4, and mrepresents an integer of 2 or more, and

in the general formula (3), M¹ and M² each independently represents ahydrogen atom or a cation.

An image display device of the present invention includes at least oneadhesive optical film having an adhesive layer, the adhesive layer beingmade of an adhesive composition that includes, as raw monomers, an alkyl(meth)acrylate ester whose alkyl group has 4 to 18 carbon atoms, acarboxyl group-containing vinyl monomer, a phosphoric acidgroup-containing vinyl monomer represented by the following generalformula (1), and a copolymerizable vinyl monomer which is optionallycopolymerizable with the above monomers, wherein with respect to aproportion of the raw monomers, an amount of the alkyl (meth) acrylateester is from 60 to 99 parts by weight based on 100 parts by weight ofthe total amount of the raw monomers, and a total proportion of thecarboxyl group-containing vinyl monomer, the phosphoric acidgroup-containing vinyl monomer and the copolymerizable vinyl monomer isfrom 1 to 40 parts by weight based on 100 parts by weight of the totalamount of the raw monomers, and a carboxyl group concentration is from0.05 to 1.50 mmol/g and a phosphoric acid group concentration is from0.01 to 0.45 mmol/g in the raw monomers:

in the general formula (1), R¹ represents a hydrogen atom or a methylgroup, R² represents a polyoxyalkylene group represented by thefollowing general formula (2), and X represents a phosphoric acid groupor a salt thereof represented by the following general formula (3)

in the general formula (2), n represents an integer of 1 to 4, and mrepresents an integer of 2 or more, and

in the general formula (3), M¹ and M² each independently represents ahydrogen atom or a cation.

An adhesive optical film of the present invention comprises an opticalfilm; an adhesive layer laminated on at least one surface of the opticalfilm; and an under coat layer containing an oxazoline group-containingpolymer, which is interposed between the optical film and the adhesivelayer.

In the adhesive optical film of the present invention, the under coatlayer is preferably made of a mixture of an oxazoline group-containingpolymer and a polyamine-based polymer.

In the adhesive optical film of the present invention, the under coatlayer is preferably made of a mixture of an oxazoline group-containingpolymer and a compound having a plurality of carboxyl groups.

In the adhesive optical film of the present invention, the under coatlayer is preferably made of a mixture of an oxazoline group-containingpolymer, a polyamine-based polymer, and a compound having a plurality ofcarboxyl groups.

In the adhesive optical film of the present invention, the oxazolinegroup-containing polymer preferably has a principal chain being of anacryl skeleton, and has an oxazoline group in a side chain of theprincipal chain.

In the adhesive optical film of the present invention, thepolyamine-based polymer preferably has a principal chain being of anacryl skeleton, and has a polyethyleneimine chain in a side chain of theprincipal chain.

In the adhesive optical film of the present invention, the compoundhaving a plurality of carboxyl groups preferably has a number averagemolecular weight of 1000 or more.

In the adhesive optical film of the present invention, the under coatlayer is preferably made of a water dispersible polymer.

In the adhesive optical film of the present invention, the adhesivelayer is preferably made of an acrylic adhesive.

In the adhesive optical film of the present invention, the acrylicadhesive is preferably water dispersible.

In the adhesive optical film of the present invention, the adhesivelayer preferably has a functional group which reacts with an oxazolinegroup and/or an amino group.

In the adhesive optical film of the present invention, the functionalgroup, which reacts with an oxazoline group and/or an amino group, ispreferably a carboxyl group.

The adhesive optical film of the present invention comprises an opticalfilm, an adhesive layer laminated on at least one surface of the opticalfilm, and an under coat layer interposed between the optical film andthe adhesive layer, the adhesive layer being made of an adhesivecomposition comprising, as raw monomers, an alkyl (meth)acrylate esterwhose alkyl group has 4 to 18 carbon atoms, a carboxyl group-containingvinyl monomer, a phosphoric acid group-containing vinyl monomerrepresented by the following general formula (1), and a copolymerizablevinyl monomer which is optionally copolymerizable with the abovemonomers, wherein, with respect to the proportion of the raw monomers,the amount of the alkyl (meth)acrylate ester is from 60 to 99 parts byweight based on 100 parts by weight of the total amount of the rawmonomers, and the total proportion of the carboxyl group-containingvinyl monomer, the phosphoric acid group-containing vinyl monomer andthe copolymerizable vinyl monomer is from 1 to 40 parts by weight, basedon 100 parts by weight of the total amount of the raw monomers, and thecarboxyl group concentration is from 0.05 to 1.50 mmol/g and thephosphoric acid group concentration is from 0.01 to 0.45 mmol/g in theraw monomers, and the under coat layer has an oxazoline group-containingmonomer.

in the general formula (1), R¹ represents a hydrogen atom or a methylgroup, R² represents a polyoxyalkylene group represented by thefollowing general formula (2), and X represents a phosphoric acid groupor a salt thereof represented by the following general formula (3),

in the general formula (2), n represents an integer of 1 to 4, and mrepresents an integer of 2 or more, and

in the general formula (3), M¹ and M² each independently represents ahydrogen atom or a cation.

In the adhesive composition of the adhesive optical film of the presentinvention, with respect to the proportion of the raw monomers, theamount of the alkyl (meth)acrylate ester is preferably from 60 to 99parts by weight, the amount of the carboxyl group-containing vinylmonomer is preferably from 0.5 to 15 parts by weight, the amount of thephosphoric acid group-containing vinyl monomer is preferably from 0.5 to20 parts by weight, and the amount of the copolymerizable vinyl monomeris preferably 39 parts by weight or less, based on 100 parts by weightof the total amount of the raw monomers.

In the adhesive optical film of the present invention, it is preferablethat the adhesive composition further contains, as the copolymerizablevinyl monomer, an alkoxysilyl group-containing vinyl monomer, the amountbeing from 0.001 to 1 parts by weight based on 100 parts by weight ofthe total amount of the raw monomers.

In the adhesive optical film of the present invention, the adhesivecomposition is preferably a water dispersible adhesive composition.

In the adhesive optical film of the present invention, the under coatlayer is preferably made of a mixture of an oxazoline group-containingpolymer and a compound having a plurality of carboxyl groups.

In the adhesive optical film of the present invention, preferably theoxazoline group-containing polymer has a principal chain being an acrylskeleton, and has an oxazoline group in a side chain of the principalchain.

In the adhesive optical film of the present invention, the compoundhaving a plurality of carboxyl groups preferably has a number averagemolecular weight of 1000 or more.

The image display device of the present invention includes ab opticalfilm an adhesive layer laminated on at least one surface of the opticalfilm, and at least one adhesive optical film having an under coat layerinterposed between the optical film and the adhesive layer, the adhesivelayer being made of an adhesive composition comprising, as raw monomers,an alkyl (meth)acrylate ester whose alkyl group has 4 to 18 carbonatoms, a carboxyl group-containing vinyl monomer, a phosphoric acidgroup-containing vinyl monomer represented by the following generalformula (1), and a copolymerizable vinyl monomer which is optionallycopolymerizable with the above monomers, wherein with respect to aproportion of the raw monomers, an amount of the alkyl (meth) acrylateester is from 60 to 99 parts by weight based on 100 parts by weight ofthe total amount of the raw monomers, and a total proportion of thecarboxyl group-containing vinyl monomer, the phosphoric acidgroup-containing vinyl monomer and the copolymerizable vinyl monomer isfrom 1 to 40 parts by weight based on 100 parts by weight of the totalamount of the raw monomers, and a carboxyl group concentration is from0.05 to 1.50 mmol/g and a phosphoric acid group concentration is from0.01 to 0.45 mmol/g in the raw monomers:

in the general formula (1), R¹ represents a hydrogen atom or a methylgroup, R² represents a polyoxyalkylene group represented by thefollowing general formula (2), and X represents a phosphoric acid groupor a salt thereof represented by the following general formula (3)

in the general formula (2), n represents an integer of 1 to 4, and mrepresents an integer of 2 or more, and

in the general formula (3), M¹ and M² each independently represents ahydrogen atom or a cation.

The adhesive composition of the present invention and the adhesiveoptical film comprising an adhesive layer made of the adhesivecomposition can achieve excellent adhesion because of high adhesion to aglass substrate.

Since the adhesive optical film of the present invention has highadhesion between an adhesive layer and an optical film, an occurrence ofan adhesive residue and a lack of adhesive can be effectively suppressedwhen sticked onto a liquid crystal display.

Furthermore, since the adhesive composition of the present invention andthe adhesive optical film comprising an adhesive layer made of theadhesive composition have excellent heat resistance and moist heatresistance, excellent durability can be obtained even in not only a hightemperature atmosphere but also a high-temperature and high-humidityatmosphere.

Therefore, the image display device of the present invention comprisingthe adhesive optical film of the present invention can realize excellentdurability.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an enlarged sectional view showing an embodiment of anadhesive optical film according to the present invention.

FIG. 2 is an enlarged sectional view showing another embodiment of anadhesive optical film according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The adhesive composition of the present invention is a water dispersibleadhesive composition comprising, as raw monomers, an alkyl(meth)acrylate ester whose alkyl group has 4 to 18 carbon atoms, acarboxyl group-containing vinyl monomer, a phosphoric acidgroup-containing vinyl monomer represented by the following generalformula (1), and a copolymerizable vinyl monomer which is optionallycopolymerizable with the above monomers, wherein, with respect to theproportion of the raw monomers, an amount of the alkyl (meth)acrylateester is from 60 to 99 parts by weight based on 100 parts by weight ofthe total amount of the raw monomers, and a total amount of the carboxylgroup-containing vinyl monomer, the phosphoric acid group-containingvinyl monomer and the copolymerizable vinyl monomer is from 1 to 40parts by weight based on 100 parts by weight of the total amount of theraw monomers, and a carboxyl group concentration is from 0.05 to 1.50mmol/g and a phosphoric acid group concentration is from 0.01 to 0.95mmol/g in the raw monomers:

in the general formula (1), R¹ represents a hydrogen atom or a methylgroup, R² represents a polyoxyalkylene group, and X represents aphosphoric acid group or a salt thereof.

The alkyl (meth)acrylate ester whose alkyl group has 4 to 18 carbonatoms may be an alkyl methacrylate ester and/or an alkyl acrylate ester,and examples thereof include alkyl (linear or branched alkyl having 4 to18 carbon atoms) (meth)acrylate esters such as butyl (meth)acrylate,isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl(meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl(meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate,nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate,isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate,tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl(meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate andoctadecyl (meth)acrylate. These alkyl (meth)acrylate esters may beappropriately used alone or in combination. For example, a mixing ratio(weight ratio) is from 1/99 to 55/45 (butyl acrylate/2-ethylhexylacrylate), and preferably from 5/95 to 60/40.

The amount of the alkyl (meth)acrylate ester is, for example, from 60 to99 parts by weight, preferably 70 to 99 parts by weight, more preferablyfrom 80 to 99 parts by weight, and particularly preferably from 80 to 98parts by weight, based on 100 parts by weight of the total amount of theraw monomers.

The carboxyl group-containing vinyl monomer may be a vinyl monomerhaving a carboxyl group in the molecule, and examples thereof includeunsaturated carboxylic acids such as (meth)acrylic acid, fumaric acid,maleic acid, itaconic acid, crotonic acid and cinnamic acid; unsaturateddicarboxylic acid monoesters such as monomethyl itaconate, monobutylitaconate and 2-acryloyloxyethylphthalic acid; unsaturated tricarboxylicacid monoesters such as 2-methacryloyloxyethyltrimellitic acid and2-methacryloyloxyethylpyromellitic acid; and carboxyalkyl acrylates suchas β-carboxyethyl acrylate, carboxypentyl acrylate andω-carboxy-polycaprolactone monoacrylate.

Examples of the carboxyl group-containing vinyl monomer includeunsaturated dicarboxylic acid anhydrides such as itaconic anhydride,maleic anhydride and fumaric anhydride.

These carboxyl group-containing vinyl monomers are appropriately usedalone or in combination.

The carboxyl group concentration of the carboxyl group-containing vinylmonomer in the raw monomers is, for example, from 0.05 to 1.50 mmol/g,and preferably from 0.20 to 0.90, mmol/g. To adjust the carboxyl groupconcentration of the carboxyl group-containing vinyl monomer within theabove range, the proportion of the carboxyl group-containing vinylmonomer is set, for example, from 0.4 to 41 parts by weight, andpreferably from 1.4 to 25 parts by weight, based on 100 parts by weightof the total amount of the raw monomers, although it varies depending onthe molecular weight of the carboxyl group-containing vinyl monomer. Theproportion of the carboxyl group-containing vinyl monomer can beadjusted, for example, from 0.5 to 15 parts by weight, preferably from0.5 to 10 parts by weight, and more preferably from 1 to 10 parts byweight, based on 100 parts by weight of the total amount of the rawmonomers, within the above carboxyl group concentration. When the amountis less than the above range, the cohesive force of the waterdispersible adhesive composition decreases. On the other hand, when theamount is more than the above range, stability upon emulsionpolymerization and water resistance of the water dispersible adhesivecomposition deteriorate.

The carboxyl group concentration of the carboxyl group-containing vinylmonomer is calculated by the following equation.Carboxyl group concentration [mmol/g]=1000×{(mixture weight [g] ofcarboxyl group-containing vinyl monomer)/(molecular weight [g/mol] ofcarboxyl group-containing vinyl monomer)}/(total weight [g] of rawmonomers)

In the above equation, the total weight of the raw monomers is theweight which does not include water, initiators, emulsifiers, chaintransfer agents and crosslinking agents, and additives such as viscositymodifiers described below.

The phosphoric acid group-containing vinyl monomer represented by thefollowing general formula (1) is a polyalkylene oxide (meth)acrylatephosphate ester,

in the general formula (1), R¹ represents a hydrogen atom or a methylgroup, R² represents a polyoxyalkylene group, and X represents aphosphoric acid group or a salt thereof.

The polyoxyalkylene group represented by R² is represented by thefollowing general formula (2):

in the general formula (2), n represents an integer of 1 to 4, and mrepresents an integer of 2 or more, and examples thereof includepolyoxyethylene group (in the general formula (2), n=2),polyoxypropylene group (in the general formula (2), n=3) and a random,block or graft unit thereof. The polymerization degree of theseoxyalkylene groups, namely m in the general formula (2), is preferably 4or more, and usually 40 or less.

When the polymerization degree of the oxyalkylene group is higher,mobility of a side chain of the phosphoric acid group increases, andinteraction with glass rapidly proceeds, and thus adhesion of the waterdispersible adhesive composition to a glass substrate is improved.

The phosphoric acid group or a salt thereof represented by X isrepresented by the following general formula (3):

in the general formula (3), M¹ and M² each independently represents ahydrogen atom or a cation.

The cation is not specifically limited and examples thereof includeinorganic cations of alkali metals such as sodium and potassium, andalkali earth metals such as calcium and magnesium; and organic cationsof quaternary amines.

As the phosphoric acid group-containing vinyl monomer, commerciallyavailable products can be used, and examples thereof includemono[poly(ethylene oxide)methacrylate]phosphate esters such as SipomerPAM-100 (manufactured by Rhodia Nicca, Ltd.), Phosmer PE (manufacturedby Uni-Chemical Co., Ltd.), Phosmer PEH (manufactured by Uni-ChemicalCo., Ltd.) and Phosmer PEDM (manufactured by Uni-Chemical Co., Ltd.);and mono[poly(propylene oxide)methacrylate]phosphate esters such asSipomer PAM-200 (manufactured by Rhodia Nicca, Ltd.), Phosmer PP(manufactured by Uni-Chemical Co., Ltd.), Phosmer PPH (manufactured byUni-Chemical Co., Ltd.) and Phosmer PPDM (manufactured by Uni-ChemicalCo., Ltd.).

These phosphoric acid group-containing vinyl monomers are appropriatelyused alone or in combination.

The phosphoric acid group concentration of the phosphoric acidgroup-containing vinyl monomer in the raw monomers is, for example, from0.01 to 0.45 mmol/g, and preferably from 0.02 to 0.20 mmol/g. To adjustthe phosphoric acid group concentration of the phosphoric acidgroup-containing vinyl monomer within the above range, the proportion ofthe phosphoric acid group-containing vinyl monomer is set from 0.4 to 22parts by weight, and preferably from 0.8 to 10 parts by weight, based on100 parts by weight of the total amount of the raw monomers, although itvaries depending on the molecular weight of the phosphoric acidgroup-containing vinyl monomer. The proportion of the phosphoric acidgroup-containing vinyl monomer can also be set from 0.5 to 20 parts byweight, preferably from 0.5 to 10 parts by weight, and more preferablyfrom 1 to 5 parts by weight, based on 100 parts by weight of the totalamount of the raw monomers, within the above phosphoric acid groupconcentration. When the amount is less than the above range, sufficienteffect of improving adhesion to the glass substrate is not archived. Onthe other hand, when the amount is more than the above range, stabilityin emulsion polymerization may deteriorate and adhesion may deterioratedue to increased elastic modulus of the water dispersible adhesivecomposition.

The phosphoric acid group concentration of the phosphoric acidgroup-containing vinyl monomer is calculated by the following equation.Phosphoric acid group concentration [mmol/g]=1000×{(mixture weight [g]of phosphoric acid group-containing vinyl monomer)/(molecular weight[g/mol] of phosphoric acid group-containing vinyl monomer)}/(totalweight [g] of raw monomers)

The total weight of the raw monomers is the weight which does notinclude water, initiators, emulsifiers, chain transfer agents andcrosslinking agents, and additives such as viscosity modifiers describedbelow.

Examples of the copolymerizable vinyl monomer copolymerizable with themonomers include functional group-containing vinyl monomers other thancarboxylic acid.

Examples of the functional group-containing vinyl monomer include vinylcarboxylate esters such as vinyl acetate and vinyl propionate; hydroxylgroup-containing vinyl monomers such as 2-hydroxyethyl acrylate,2-hydroxypropyl acrylate and 2-hydroxybutyl acrylate; amidegroup-containing unsaturated monomers such as (meth)acrylamide,N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide,N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide,N-methoxymethyl(meth)acrylamide, N-methylol(meth)acrylamide,N-methylolpropane(meth)acrylamide and N-vinylcarboxylic acid amide;glycidyl group-containing unsaturated monomers such as glycidyl(meth)acrylate and methyl glycidyl (meth)acrylate; cyanogroup-containing unsaturated monomers such as acrylonitrile andmethacrylonitrile; isocyanate group-containing unsaturated monomers suchas 2-methacryloyloxyethyl isocyanate; sulfonic acid group-containingunsaturated monomers such as styrenesulfonic acid, allylsulfonic acid,2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl (meth)acrylate and (meth)acryloyloxynaphthalenesulfonic acid; maleimide-based monomers such asN-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide andN-phenylmaleimide; itaconimide-based monomers such asN-methylitaconimide, N-ethylitaconimide, N-butylitaconimide,N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimideand N-laurylitaconimide; succinimide-based monomers such asN-(meth)acryloyloxymethylenesuccinimide,N-(meth)acryloyl-6-oxyhexamethylenesuccinimide andN-(meth)acryloyl-8-oxyoctamethylenesuccinimide; and glycol-based acrylester monomers such as (meth)acrylic acid polyethylene glycol,(meth)acrylic acid polypropylene glycol, (meth)acrylic acidmethoxyethylene glycol and (meth)acrylic acid methoxypolypropyleneglycol.

Examples of the functional group-containing vinyl monomer includepolyfunctional monomer.

Examples of the polyfunctional monomer include (mono or poly)alkyleneglycol di(meth)acrylates, for example, (mono or poly)ethylene glycoldi(meth)acrylates such as ethylene glycol di(meth)acrylate, diethyleneglycol di(meth)acrylate, triethylene glycol di(meth)acrylate,trimethylolpropane tri(meth)acrylate and tetraethylene glycoldi(meth)acrylate, and mono or poly)propylene glycol di(meth)acrylatessuch as propylene glycol di(meth)acrylate; neopentyl glycoldi(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritoldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritoltri(meth)acrylate, dipentaerythritol hexa(meth)acrylate and divinylbenzene. Examples of the polyfunctional monomer include epoxy acrylate,polyester acrylate and urethane acrylate.

Examples of the copolymerizable vinyl monomer include the abovefunctional group-containing vinyl monomers; aromatic vinyl monomers suchas styrene; alkyl (linear or branched alkyl having 1 to 3 carbon atoms)(meth)acrylate esters such as methyl (meth)acrylate, ethyl(meth)acrylatee, propyl (meth)acrylate and isopropyl (meth)acrylate;(meth)acrylic acid alicyclic hydrocarbone esters such as cyclohexyl(meth)acrylate, bornyl (meth)acrylate and isobornyl (meth)acrylate; aryl(meth)acrylate esters such as phenyl (meth)acrylate; alkoxygroup-containing unsaturated monomers such as methoxyethyl(meth)acrylate and ethoxyethyl (meth)acrylate; olefin-based monomerssuch as ethylene, propylene, isoprene, butadiene and isobutylene; vinylether-based monomers such as vinyl ether; halogen atom-containingunsaturated monomers such as vinyl chloride; vinyl group-containingheterocyclic compounds such as N-vinyl pyrrolidone, N-(1-methylvinyl)pyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine,N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole,N-vinyloxazole, N-vinylmorpholin and tetrahydrofurfuryl (meth)acrylate;and acrylate ester-based monomers containing a halogen atom such asfluorine atom, such as fluorine (meth)acrylate.

Examples of the copolymerizable vinyl monomer include alkoxysilylgroup-containing vinyl monomer. Examples of the alkoxysilylgroup-containing vinyl monomer include silicone-based (meth)acrylatemonomer and silicone-based vinyl monomer.

Examples of the silicone-based (meth)acrylate monomer include(meth)acryloyloxyalkyl-trialkoxysilanes such as (meth)acryloyloxymethyl-trimethoxysilane,(meth)acryloyloxymethyl-triethoxysilane, 2-(meth)acryloyloxyethyl-trimethoxysilane,2-(meth)acryloyloxyethyl-triethoxysilane, 3-(meth)acryloyloxypropyl-trimethoxysilane,3-(meth)acryloyloxypropyl-triethoxysilane,3-(meth)acryloyloxypropyl-tripropoxysilane,3-(meth)acryloyloxypropyl-triisopropoxysilane and3-(meth)acryloyloxypropyl-tributoxysilane;(meth)acryloyloxyalkyl-alkyldialkoxysilanes such as (meth)acryloyloxymethyl-methyldimethoxysilane,(meth)acryloyloxymethyl-methyldiethoxysilane,2-(meth)acryloyloxyethyl-methyldimethoxysilane,2-(meth)acryloyloxyethyl-methyldiethoxysilane, 3-(meth)acryloyloxypropyl-methyldimethoxysilane,3-(meth)acryloyloxypropyl-methyldiethoxysilane,3-(meth)acryloyloxypropyl-methyldipropoxysilane,3-(meth)acryloyloxypropyl-methyldiisopropoxysilane,3-(meth)acryloyloxypropyl-methyldibutoxysilane,3-(meth)acryloyloxypropyl-ethyldimethoxysilane,3-(meth)acryloyloxypropyl-ethyldiethoxysilane,3-(meth)acryloyloxypropyl-ethyldipropoxysilane,3-(meth)acryloyloxypropyl-ethyldiisopropoxysilane,3-(meth)acryloyloxypropyl-ethyldibutoxysilane,3-(meth)acryloyloxypropyl-propyldimethoxysilane and3-(meth)acryloyloxypropyl-propyldiethoxysilane; and(meth)acryloyloxyalkyl-dialkyl(mono)alkoxysilanes corresponding to thesemonomers.

Examples of the silicone-based vinyl monomer includevinyltrialkoxysilanes such as vinyltrimethoxysilane,vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilaneand vinyltributoxysilane, and vinylalkyldialkoxysilane andvinyldialkylalkoxysilane corresponding to these monomers;vinylalkyltrialkoxysilanes such as vinylmethyltrimethoxysilane,vinylmethyltriethoxysilane, β-vinylethyltrimethoxysilane,β-vinylethyltriethoxysilane, γ-vinylpropyltrimethoxysilane,γ-vinylpropyltriethoxysilane, γ-vinylpropyltripropoxysilane,γ-vinylpropyltriisopropoxysilane and γ-vinylpropyltributoxysilane, and(vinylalkyl)alkyldialkoxysilane and(vinylalkyl)dialkyl(mono)alkoxysilane corresponding to these monomers.

These copolymerizable vinyl monomers are appropriately used alone or incombination.

Among these copolymerizable vinyl monomers, an alkoxysilylgroup-containing vinyl monomer is preferable.

By using the alkoxysilyl group-containing vinyl monomer as thecopolymerizable vinyl monomer, alkoxysilyl groups are introduced in thepolymer chain and a crosslinked structure can be formed by the reactionbetween them. Particularly in the water dispersible adhesivecomposition, since a ununiform crosslinked structure is formed in caseof using the following described crosslinking agent, terminal peelingmay more easily occur. However, when the alkoxysilyl group-containingmonomer is used, a uniform crosslinked structure can be formed and thusadhesion and fixation to the glass substrate can be improved. Further,adhesion to the glass substrate can be enhanced by an interactionbetween the alkoxysilyl group and the glass substrate.

If necessary, the copolymerizable vinyl monomer is optionally mixed andthe proportion thereof is, for example, 39 parts by weight or less,preferably 19 parts by weight or less, and more preferably 18 parts byweight or less, based on 100 parts by weight of the total amount of theraw monomers. When the copolymerizable vinyl monomer is an alkoxysilylgroup-containing vinyl monomer, the proportion thereof is, for example,from 0.001 to 1 parts by weight, preferably from 0.005 to 0.1 parts byweight, and more preferably from 0.01 to 0.1 parts by weight, based on100 parts by weight of the total amount of the raw monomers. When theamount of the alkoxysilyl group-containing vinyl monomer is less thanthe above range, a cohesive force of the water dispersible adhesivecomposition decreases and adhesion between the water dispersibleadhesive composition and the glass substrate can not be improved becauseof poor crosslinking due to the alkoxysilyl group. On the other hand,when the amount is more than the above range, stability in emulsionpolymerization and adhesion may deteriorate.

The total amount of the carboxyl group-containing vinyl monomer, thephosphoric acid group-containing vinyl monomer and the copolymerizablevinyl monomer among the raw monomers described above is, for example,from 1 to 40 parts by weight, preferably from 1 to 30 parts by weight,more preferably from 1 to 20 parts by weight, and particularlypreferably from 2 to 20 parts by weight, based on 100 parts by weight ofthe total amount of the raw monomers.

The water dispersible adhesive composition is prepared by copolymerizingthe above raw monomers using a polymerization method such as emulsionpolymerization.

In the emulsion polymerization, the above raw monomers, polymerizationinitiators, emulsifiers and, if necessary, chain transfer agents areappropriately mixed in water and then copolymerized. More specifically,known emulsion polymerization methods such as collective charging method(collective polymerization method), monomer dropping method and monomeremulsion dropping method can be employed. In the monomer droppingmethod, continuous dropping or divisional dropping is appropriatelyselected. Reaction conditions are appropriately selected, but thepolymerization temperature is, for example, from 20 to 90° C.

The polymerization initiator is not specifically limited and apolymerization initiator, which is usually used in the emulsionpolymerization, is used. Examples thereof include azo-based initiatorssuch as 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methylpropioneamidine) disulfate,2,2′-azobis(2-methylpropioneamidine) dihydrochloride,2,2′-azobis(2-amidinopropane) dihydrochloride,2,2′-azobis[N-(2-carboxyethyl)-2-methylpropioneamidine]hydrate,2,2′-azobis(N,N′-dimethyleneisobutylamidine) and2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride;persulfate-based initiators such as potassium persulfate and ammoniumpersulfate; peroxide-based initiators such as benzoyl peroxide, t-butylhydroperoxide and hydrogen peroxide; substituted ethane-based initiatorssuch as phenyl-substituted ethane; carbonyl-based initiator such asaromatic carbonyl compound; and redox-based initiator such ascombination of persulfate and sodium hydrogen sulfite and combination ofperoxide and sodium ascorbate.

These polymerization initiators are appropriately used alone or incombination.

Among these polymerization initiators, azo-based initiators arepreferably used.

The amount of the polymerization initiator is appropriately selected andis from 0.005 to 1 parts by weight based on 100 parts by weight of thetotal amount of the raw monomers.

The dissolved oxygen concentration in the monomer solution may bedecreased by replacing the atmosphere with nitrogen before or whilemixing the polymerization initiator with the raw monomers.

The emulsifier is not specifically limited and a known emulsifier, whichis usually used in the emulsion polymerization, is used. Examplesthereof include anionic emulsifiers such as sodium lauryl sulfate,ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylenesodium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate,ammonium polyoxyethylene alkyl phenyl ether sulfate, sodiumpolyoxyethylene alkyl phenyl ether sulfate and sodium polyoxyethylenealkyl sulfosuccinate; and nonionic emulsifiers such as polyoxyethylenealkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fattyacid ester and polyoxyethylene polyoxypropylene block polymer.

The emulsifier further includes radical polymerizable (reactive)emulsifiers (for example, HS-10 (manufactured by Dai-Ichi Kogyo SeiyakuCo., Ltd.) and LATEMUL PD-104 (manufactured by Kao Corporation)) inwhich a radical polymerizable functional group (reactive group) such aspropenyl group or allyl ether group is introduced into the anionicemulsifier and the nonionic emulsifier.

These emulsifiers are appropriately used alone or in combination. Theamount of the emulsifier is from 0.2 to 10 parts by weight, andpreferably from 0.5 to 5 parts by weight, based on 100 parts by weightof the total amount of the raw monomers.

If necessary, the chain transfer agent is used to adjust a molecularweight of the water dispersible adhesive composition and a chaintransfer agent, which is usually used in the emulsion polymerization, isused. Examples thereof include mercaptanes such as 1-dodecanethiol,mercaptoacetic acid, 2-mercaptoethanol, 2-ethylhexyl thioglycolate and2,3-dimethylcapto-1-propanol.

These chain transfer agents are appropriately used alone or incombination. The proportion of the chain transfer agent is from 0.001 to0.5 parts by weight based on 100 parts by weight of the total amount ofthe raw monomers.

The copolymer resulted from the above-mentioned emulsion polymerizationcan be prepared as an emulsion (water dispersion) of the waterdispersible adhesive composition.

The water dispersible adhesive composition can also be prepared bypolymerizing the raw monomers through a method of using no organicsolvent other than the emulsion polymerization method, and dispersingthe resulting polymer in water using the above emulsifier.

The water dispersible adhesive composition may be mixed with acrosslinking agent according to the purposes and applications. Examplesof the crosslinking agent include isocyanate-based crosslinking agent,epoxy-based crosslinking agent, oxazoline-based crosslinking agent,aziridine-based crosslinking agent and metal chelate-based crosslinkingagent. These crosslinking agents are not specifically limited and an oilsoluble or water soluble crosslinking agent is used. These crosslinkingagents are appropriately used alone or in combination. The proportionis, for example, from 0.1 to 10 parts by weight based on 100 parts byweight of the total amount of the raw monomers.

For the purpose of improving stability of the emulsion, a pH of thewater dispersible adhesive composition is adjusted from 7 to 9, andpreferably from 7 to 8, by ammonia water or the like.

Furthermore, additives, which are usually added to a water dispersibleadhesive composition, such as viscosity modifiers and, if necessary,release modifiers, plasticizers, softeners, fillers, colorant (forexample, pigments, dyes), antioxidant and surfactant may beappropriately added to the water dispersible adhesive composition. Theproportion of these additives is not specifically limited and can beappropriately selected.

The viscosity modifier is not specifically limited and examples thereofinclude acrylic thickener.

The gel fraction of the water dispersible adhesive composition (solidcontent) is, for example, from 50 to 100% by weight, and preferably from70 to 100% by weight. When the gel fraction is less than the aboverange, foaming and peeling may occur in case the water dispersibleadhesive composition is applied to the adhesive optical film and theresulting product is used in a high-temperature and high-humidityatmosphere.

The gel fraction can be calculated by the following equation after thewater dispersible adhesive composition was coated with aTeflon(trademark) sheet and immersed in ethyl acetate for 7 days.Gel fraction(% by weighting)=(weight of water dispersible adhesivecomposition adhering to Teflon sheet after immersing/weight of waterdispersible adhesive composition before immersing)×100

Also in case of bonding the water dispersible adhesive composition ofthe present invention to the glass substrate, the adhesive optical filmcan be firmly bonded to the glass substrate because of high adhesion.

The adhesive optical film of the present invention includes a firstadhesive optical film comprising an adhesive layer made of the aboveadhesive composition and an optical film described hereinafter; and asecond adhesive optical film comprising an optical film, an adhesivelayer laminated on at least one side of the optical film and an undercoat layer interposed between the optical film and the adhesive layer.

In the second adhesive optical film, an adhesive used in the adhesivelayer is usually used in the adhesive layer, and examples thereofinclude acrylic adhesive and natural rubber latex-based adhesive. Theadhesive is preferably an acrylic adhesive, and more preferably a waterdispersible acrylic adhesive.

The acrylic adhesive contains an alkyl (meth)acrylate ester as itsmonomer component.

The alkyl (meth)acrylate ester includes a compound represented by thefollowing general formula (4):H₂C═CR³COOR⁴  (4)in the general formula (4), R³ represents a hydrogen atom or a methylgroup, and R⁴ represents a linear or branched alkyl group having 1 to 18carbon atoms.

Examples of the substituent represented by R⁴ include methyl group,ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,sec-butyl group, t-butyl group, pentyl group, neopentyl group, isoamylgroup, hexyl group, heptyl group, octyl group, 2-ethylhexyl group,isooctyl group, nonyl group, isononyl group, decyl group, isodecylgroup, undecyl group, dodecyl group, tridecyl group, tetradecyl group,pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group.

The alkyl (meth)acrylate ester is specifically an alkyl methacrylateester and/or an alkyl acrylate ester, and examples thereof include alkyl(linear or branched alkyl having 1 to 18 carbon atoms) (meth)acrylateesters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl(meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl(meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl(meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl(meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl(meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl(meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate,hexadecyl (meth)acrylate, heptadecyl (meth)acrylate and octadecyl(meth)acrylate. These alkyl (meth)acrylate ester are appropriately usedalone or in combination. For example, butyl acrylate may be used incombination with 2-ethylhexyl acrylate and the mixing ratio (weightratio) is, for example, from 1/99 to 55/45 (butyl acrylate/2-ethylhexylacrylate), and preferably from 5/95 to 60/40.

The proportion of the alkyl (meth)acrylate ester is 80 parts by weightor more, preferably 85 parts by weight or more, and more preferably 90parts by weight or more, based on 100 parts by weight of the entiremonomer components.

For the purpose of improving adhesion to the adherend of the adhesivelayer by introducing a crosslink point (functional group) for thermalcrosslinking, the acrylic adhesive preferably contains, as a monomercomponent, a functional group-containing monomer, in addition to thealkyl (meth)acrylate ester.

Examples of the functional group-containing monomer include carboxylgroup-containing unsaturated monomers such as (meth)acrylic acid,itaconic acid, maleic acid, fumaric acid and crotonic acid; acidanhydride group-containing unsaturated monomers such as itaconicanhydride, maleic anhydride and fumaric anhydride; hydroxylgroup-containing unsaturated monomers such as 2-hydroxyethyl acrylate,2-hydroxypropyl acrylate and 2-hydroxybutyl acrylate; amidegroup-containing unsaturated monomers such as (meth)acrylamide,N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide,N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide,N-methoxymethyl(meth)acrylamide, N-methylol(meth)acrylamide andN-methylolpropane(meth)acrylamide; amino group-containing unsaturatedmonomers such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate and t-butylaminoethyl (meth)acrylate; glycidylgroup-containing unsaturated monomers such as glycidyl (meth)acrylateand methyl glycidyl (meth)acrylate; cyano group-containing unsaturatedmonomers such as (meth)acrylonitrile; maleimide group-containingmonomers such as N-cyclohexylmaleimide, N-isopropylmaleimide,N-laurylmaleimide and N-phenylmaleimide; itaconimide group-containingmonomers such as N-methylitaconimide, N-ethylitaconimide,N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide,N-cyclohexylitaconimide and N-laurylitaconimide; succinimidegroup-containing monomers such asN-(meth)acryloyloxymethylenesuccinimide,N-(meth)acryloyl-6-oxyhexamethylenesuccinimide andN-(meth)acryloyl-8-oxyoctamethylenesuccinimide; vinyl group-containingheterocyclic compounds such as N-vinyl pyrrolidone,N-(1-methylvinyl)pyrrolidone, N-vinylpyridine, N-vinylpiperidone,N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole,N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine and(meth)acryloylmorpholine; sulfonic acid group-containing unsaturatedmonomers such as styrenesulfonic acid, allylsulfonic acid,2-(meth)acrylamide-2-methylpropanesulfonic acid,(meth)acrylamidepropanesulfonic acid, sulfopropyl(meth)acrylate and(meth) acryloyloxynaphthalenesulfonic acid; phosphoric acidgroup-containing unsaturated monomers such as 2-hydroxyethylacryloylphosphate; functional monomers such as 2-methacryloyloxyethylisocyanate, and N-vinylcarboxylic acid amide.

The functional group-containing monomer further includes apolyfunctional monomer.

Examples of the polyfunctional monomer include the same as thosedescribed above.

These functional group-containing monomers are appropriately used aloneor in combination.

Among these functional group-containing monomers, the carboxylgroup-containing unsaturated monomers and acid anhydridegroup-containing unsaturated monomers are preferable. In carboxylgroup-containing unsaturated monomers and acid anhydridegroup-containing unsaturated monomers, a carboxyl group contained in orgenerated from these monomers efficiently reacts with an oxazoline groupof an oxazoline group-containing polymer constituting an under coatlayer described hereinafter or an amino group of a polyamine-basedpolymer, and thus adhesion with the optical film can be enhanced.

The proportion of the functional group-containing monomer is from 0.5 to12 parts by weight, and preferably from 1 to 8 parts by weight, based on100 parts by weight of the alkyl (meth)acrylate ester.

For the purpose of improving various characteristics such as cohesiveforce, the acrylic adhesive may contain, as a monomer component, acopolymerizable monomer copolymerizable with the above alkyl(meth)acrylate ester.

Examples of the copolymerizable monomer include vinyl estergroup-containing monomers such as vinyl acetate; aromatic unsaturatedmonomers such as styrene and vinyltoluene; (meth)acrylic acid alicyclichydrocarbon ester monomers such as cyclopentyl di(meth)acrylate andisobornyl (meth)acrylate; (meth)acrylate ester monomers of polyhydricalcohol, such as neopentyl glycol di(meth)acrylate, hexanedioldi(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropanetri(meth)acrylate, tetramethylolmethane tri(meth)acrylate anddipentaerythritol hexa(meth)acrylate; alkoxy group-containingunsaturated monomer such as methoxyethyl (meth)acrylate and ethoxyethyl(meth)acrylate; olefin-based monomers such as ethylene, propylene,isoprene, butadiene and isobutylene; vinyl ether-based monomers such asvinyl ether; halogen atom-containing unsaturated monomers such as vinylchloride; and a heterocycle such as tetrahydrofurfuryl (meth)acrylate,and fluorine (meth)acrylate, acrylate ester-based monomers containing ahalogen atom.

Further, examples of the copolymerizable monomer include alkoxysilylgroup-containing vinyl monomer. Examples of the alkoxysilylgroup-containing vinyl monomer include silicone-based (meth)acrylatemonomer and silicone-based vinyl monomer. Examples of the silicone-based(meth)acrylate monomer and the silicone-based vinyl monomer include thesame as those described above.

By using the alkoxysilyl group-containing vinyl monomer as thecopolymerizable vinyl monomer, an alkoxysilyl group is introduced intothe polymer chain and a crosslinked structure can be formed by areaction between them. Particularly in case of the acrylic adhesive,since a non-uniform crosslinked structure is formed by using acrosslinking agent described hereinafter, terminal peeling of theadhesive optical film is likely to occur when used in a high temperatureatmosphere. However, when the alkoxysilyl group-containing monomer isused, a uniform crosslinked structure can be formed and thus adhesionand fixation to a glass substrate of such as a liquid crystal displaycan be improved. The alkoxysilyl group interacts with a glass substrate,thus making it possible to enhance adhesion to the glass substrate.

These copolymerizable monomers are appropriately used alone or incombination.

The proportion of the copolymerizable monomer is, for example,preferably 30 parts by weight or less, and preferably 15 parts by weightor less, based on 100 parts by weight of the alkyl (meth)acrylate ester.

The method for preparing an acrylic adhesive is not specifically limitedand the acrylic adhesive is prepared by solution-polymerizing the abovemonomer component in an organic solvent or emulsion-polymerizing themonomer component in water.

In the emulsion polymerization, the above monomer component,polymerization initiators, emulsifiers, and, if necessary, chaintransfer agents are appropriately mixed and polymerized in water. Morespecifically, known emulsion polymerization methods such as collectivecharging method (collective polymerization method), monomer droppingmethod and monomer emulsion dropping method can be employed. In themonomer dropping method, continuous dropping or divisional dropping isappropriately selected. The reaction conditions are appropriatelyselected and the polymerization temperature is, for example, from 20 to90° C.

The polymerization initiator is not specifically limited and examplesthereof include the same as those described above. These polymerizationinitiators are appropriately used alone or in combination. Theproportion of the polymerization initiator is appropriately selected andis from 0.005 to 1 parts by weight based on 100 parts by weight of theentire monomer components.

As the emulsifier is not specifically limited and an emulsifier, whichis usually used in the emulsion polymerization, is used. Examplesthereof include the same anionic emulsifiers and nonionic emulsifiers asthose described above.

These emulsifiers are appropriately used alone or in combination. Theproportion of the emulsifier is, for example, from 0.2 to 10 parts byweight, and preferably from 0.5 to 5 parts by weight, based on 100 partsby weight of the entire monomer components.

The chain transfer agent is optionally used to adjust the molecularweight of the acrylic adhesive and a chain transfer agent, which isusually used in the emulsion polymerization, is used. Examples of thechain transfer agent include the same as those described above.

These chain transfer agents are appropriately used alone or incombination. The proportion of the chain transfer agent is from 0.001 to0.5 parts by weight based on 100 parts by weight of the entire monomercomponents.

The acrylic adhesive can be prepared as a water dispersible acrylicadhesive, that is, a water dispersible emulsion (water dispersion) bythe above emulsion polymerization.

The water dispersible acrylic adhesive can also be prepared bypolymerizing the above monomer component through a method other than theemulsion polymerization and dispersing the resulting polymer in waterusing the above emulsifier.

The adhesive may be mixed with a crosslinking agent according to thepurposes and applications. Examples of the crosslinking agent includethe same as those described above. As crosslinking agents are notspecifically limited a water soluble or oil soluble crosslinking agentis used. These crosslinking agents are appropriately used alone or incombination. The proportion is from 0.1 to 10 parts by weight based on100 parts by weight of the entire raw monomer components.

When the adhesive is a water dispersible adhesive, for the purpose ofimproving stability of the emulsion, the pH is adjusted, for example,from 7 to 9, and preferably from 7 to 8, by ammonia water or the like.

Furthermore, additives, which are usually added to an adhesive, such asviscosity modifiers and, if necessary, release modifiers, plasticizers,softeners, fillers, colorant (for example, pigments, dyes), antioxidantand surfactant may be appropriately added to the adhesive. Theproportion of these additives is not specifically limited and can beappropriately selected.

The viscosity modifier is not specifically limited and examples thereofinclude acrylic thickener.

The gel fraction of the solid content of the adhesive is, for example,from 50 to 100% by weight, and preferably from 70 to 100% by weight.When the gel fraction is less than the above range, foaming and peelingmay occur in case the adhesive is applied to the adhesive optical filmand the resulting product is used in a high-temperature andhigh-humidity atmosphere.

The gel fraction can be calculated in the same manner as describedabove.

In the second adhesive optical film, the adhesive may be the adhesivewhich is used in the first adhesive optical film, that is, the aboveadhesive composition of the present invention (corresponding to thethird adhesive optical film in this case).

In the second adhesive optical film, the under coat layer contains atleast an oxazoline group-containing polymer.

The oxazoline group-containing polymer has a principal chain being anacryl skeleton or a styrene skeleton, and has an oxazoline group in aside chain of the principal chain, and is preferably an oxazolinegroup-containing acrylic polymer which has a principal chain composed ofan acryl skeleton and has an oxazoline group in a side chain of theprincipal chain.

Examples of the oxazoline group include 2-oxazoline group, 3-oxazolinegroup and 4-oxazoline group, and a 2-oxazoline group is preferable.

The 2-oxazoline group is generally represented by the following generalformula (5):

in the general formula (5), R⁵, R⁶, R⁷ and R⁸ each independentlyrepresents a hydrogen atom, a halogen atom, an alkyl group, an aralkylgroup, a phenyl group or a substituted phenyl group.

The number average molecular weight of the oxazoline group-containingpolymer is, for example, 5000 or more, preferably 10000 or more and1000000 or less. When the number average molecular weight is less than5000, cohesive failure occurs because of poor strength of the under coatlayer and an anchoring force may not be improved. On the other hand,when the number average molecular weight is more than 1000000,workability may be inferior. The oxazoline value of the oxazolinegroup-containing polymer is, for example, 1500 g solid/eq. or less, andpreferably 1200 g solid/eq. or less. When the oxazoline value is morethan 1500 g solid/eq., the amount of the oxazoline group contained in amolecule decreases and the anchoring force may not be improved.

Since the oxazoline group of the oxazoline group-containing polymerreacts with a functional group (for example, carboxyl group or hydroxylgroup) contained in the adhesive at a comparatively low temperature, theoxazoline group-containing polymer reacts with the functional group inthe adhesive layer and can firmly adhere to the adhesive layer whencontained in the under coat layer.

Commercially available products are used as the oxazolinegroup-containing polymer, and specific examples thereof includeoxazoline group-containing acrylic polymers such as EPOCROS WS-500(aqueous solution type, solid content: 40%, principal chain: acrylic, pH7 to 9, oxazoline value: 220 g solid/eq., manufactured by NipponShokubai Co., Ltd.) and EPOCROS WS-700 (aqueous solution type, solidcontent: 25%, principal chain: acrylic, pH 7 to 9, oxazoline value: 220g solid/eq., manufactured by Nippon Shokubai Co., Ltd.); and oxazolinegroup-containing acryl/styrene-based polymers such as EPOCROS K-1000series (emulsion type, solid content: 40%, principal chain:styrene/acrylic, oxazoline value: 1100 g solid/eq., pH 7 to 9,manufactured by Nippon Shokubai Co., Ltd.) and EPOCROS K-2000 series(emulsion type, solid content: 40%, principal chain: styrene/acrylic, pH7 to 9, oxazoline value: 550 g solid/eq., manufactured by NipponShokubai Co., Ltd.). In view of an improvement in adhesion, an aqueoussolution-type oxazoline group-containing acrylic polymer is preferableas compared with an emollition type acrylic polymer containing anemulsifier.

Such an oxazoline group-containing acrylic polymer is excellent inaffinity with an adhesive, and therefore enhances adhesion between anoptical film and an adhesive, and thus an adhesive optical film havingexcellent heat resistance can be obtained.

Such an oxazoline group-containing polymer is generally dissolved orwater-dispersed in a solution such as organic solvent or water and isprepared as a resin solution or water dispersion containing theoxazoline group-containing polymer. In view of prevention ofdenaturation of the optical film, it is preferably prepared as a waterdispersion.

In the adhesive optical film of the present invention, the under coatlayer is preferably made of a mixture of an oxazoline group-containingpolymer and a polyamine-based polymer.

The polyamine-based polymer is a polymer having a plurality of primaryor secondary amino groups in the molecule, and examples thereof includepolyethyleneimine; polyallylamine; and ethyleneimine-modified acrylicpolymer and allylamine-modified acrylic polymer in which a principalchain composed of an acryl skeleton is contained and a polyethyleneiminechain represented by the following general formula (6) or apolyallylamine chain represented by the following general formula (7) ismodified in a side chain of the principal chain. Theethyleneimine-modified acrylic polymer is preferable.

In the general formula (6), x and y represent the polymerization degreeof a polyethyleneimine chain.

In the general formula (7), z represents the polymerization degree of apolyallylamine chain.

The number average molecular weight of the polyamine-based polymer is,for example, 200 or more, preferably 1000 or more, and more preferably8000 or more, and usually 1000000 or less is preferred. When the numberaverage molecular weight is less than 200, cohesive failure occursbecause of poor strength of the under coat layer and the anchoring forcemay not be improved. On the other hand, when the number averagemolecular weight is more than 1000000, workability may be inferior. Theamine hydrogen equivalent of the polyamine-based polymer is, forexample, 1500 g solid/eq. or less, and preferably 1200 g solid/eq. orless. When the amine hydrogen equivalent is more than 1500 g solid/eq.,the amount of the amino group contained in the molecule decreases andthe anchoring force may not be improved.

Commercially available products are used as the polyamine-based polymer,and specific examples thereof include polyethyleneimines such as EPOMINSP-003 (water soluble type, amine hydrogen equivalent: 47.6 g solid/eq.,manufactured by Nippon Shokubai Co., Ltd.), EPOMIN SP-006 (water solubletype, amine hydrogen equivalent: 50.0 g solid/eq., manufactured byNippon Shokubai Co., Ltd.), EPOMIN SP-012 (water soluble type, aminehydrogen equivalent: 52.6 g solid/eq., manufactured by Nippon ShokubaiCo., Ltd.), EPOMIN SP-018 (water soluble type, amine hydrogenequivalent: 52.6 g solid/eq., manufactured by Nippon Shokubai Co.,Ltd.), EPOMIN SP-103 (water soluble type, amine hydrogen equivalent:52.6 g solid/eq., manufactured by Nippon Shokubai Co., Ltd.), EPOMINSP-110 (water soluble type, amine hydrogen equivalent: 55.6 g solid/eq.,manufactured by Nippon Shokubai Co., Ltd.), EPOMIN SP-200 (water solubletype, amine hydrogen equivalent: 55.6 g solid/eq., manufactured byNippon Shokubai Co., Ltd.) and EPOMIN P-1000 (water soluble type, aminehydrogen equivalent: 52.6 g solid/eq., manufactured by Nippon ShokubaiCo., Ltd.); and ethyleneimine-modified acrylic polymers such as POLYMENTSK-1000 (emulsion type, amine hydrogen equivalent: 650 g solid/eq.,manufactured by Nippon Shokubai Co., Ltd.), POLYMENT NK-350 (solventtype, amine hydrogen equivalent: 1100 g solid/eq., manufactured byNippon Shokubai Co., Ltd.), POLYMENT NK-380 (solvent type, aminehydrogen equivalent: 1100 g solid/eq., manufactured by Nippon ShokubaiCo., Ltd.), POLYMENT NK-100PM (water soluble type, amine hydrogenequivalent: 350 to 450 g solid/eq., manufactured by Nippon Shokubai Co.,Ltd.) and POLYMENT NK-200PM (water soluble type, amine hydrogenequivalent: 350 to 450 g solid/eq., manufactured by Nippon Shokubai Co.,Ltd.).

The proportion of the polyamine-based polymer is, for example, from 50to 98 parts by weight, preferably from 70 to 97 parts by weight, andmore preferably from 80 to 95 parts by weight, based on 100 parts byweight of the total amount of the oxazoline group-containing polymer andthe polyamine-based polymer. When the amount of the polyamine-basedpolymer is less than 50 parts by weight, moist heat resistance may beinferior. On the other hand, when the amount of the polyamine-basedpolymer is more than 98 parts by weight, heat resistance may beinferior.

Such mixture of the oxazoline group-containing polymer and thepolyamine-based polymer is generally dissolved or water-dispersed in asolution such as organic solvent or water, and is prepared as a resinsolution or water dispersion of the mixture of the oxazolinegroup-containing polymer and the polyamine-based polymer. Preferably, itis prepared as a water dispersible mixture (water dispersible polymer)of the oxazoline group-containing polymer and the polyamine-basedpolymer in which the mixture of them is water-dispersed.

When the under coat layer is made of the mixture of the oxazolinegroup-containing polymer and the polyamine-based polymer, excellentmoist heat resistance can be imparted to the adhesive optical film whilemaintaining high adhesion and heat resistance in case the under coatlayer is made of only the oxazoline group-containing polymer, and thusan adhesive optical film having high adhesion, heat resistance and moistheat resistance can be obtained.

It is considered that such an effect is exerted by the following reason.In addition to the effect of an increase in adhesion due to a hydrogenbond of the amino group contained in the polyamine-based polymer and anacid-base interaction, the under coat layer is crosslinked by thereaction between the oxazoline group-containing polymer and thepolyamine-based polymer, thereby the under coat layer to be firm, andthus heat resistance and moist heat resistance are improved.

In the adhesive optical film of the present invention, the under coatlayer is also preferably made of a mixture of the oxazolinegroup-containing polymer and the compound having a plurality of carboxylgroups.

Examples of the compound having a plurality of carboxyl groups includesaturated low molecular compound having a plurality of carboxyl groups,for example, dicarboxylic acid compounds such as succinic acid, adipicacid and phthalic acid; and tricarboxylic acid compounds such as citricacid.

The compound having a plurality of carboxyl groups is a polymercompound, and examples thereof include polymers of unsaturated compoundssuch as acrylic acid and methacrylic acid (for example, polyacrylic acidand polymethacrylic acid). Copolymers of unsaturated compounds such ascopolymer of acrylic acid and methacrylic acid, copolymer of acrylicacid and maleic acid, copolymer of methacrylic acid and maleic acid, andcopolymer of acrylic acid, methacrylic acid and maleic acid. A copolymerof acrylic acid and maleic acid is preferable.

The number average molecular weight (measured by GPC in terms ofstandard polyethyleneglycol) of the compound having a plurality ofcarboxyl groups is 1000 or more, and preferably from 3000 to 200000.

All or portion of carboxyl groups of the compound having a plurality ofcarboxyl groups may form a salt with a cation.

Examples of the cation include inorganic cations such as potassium ionand sodium ion; and organic cations such as ammonium ion, and cations ofprimary amine, secondary amine and tertiary amine.

Commercially available products are usually used as the compound havinga plurality of carboxyl groups, and specific examples thereof includePOISE 532A (acrylic acid/maleic acid copolymer ammonium salt, numberaverage molecular weight: about 10000, manufactured by Kao Corporation).

Such mixture of the oxazoline group-containing polymer and the compoundhaving a plurality of carboxyl groups is generally dissolved orwater-dispersed in a solution such as organic solvent or water, and isprepared as a resin solution or water dispersion of the mixture of theoxazoline group-containing polymer and the compound having a pluralityof carboxyl groups. Preferably, it is prepared as a water dispersiblemixture (water dispersible polymer) of the oxazoline group-containingpolymer and the compound having a plurality of carboxyl groups in whichthe mixture of them is water-dispersed.

In case a water soluble material is used as the under coat layer, whenthe thickness of the under coat layer increases, the strength of theunder coat layer may decrease when used in a high-humidity atmosphereand interlaminar fracture may occur. However, when the under coat layeris made of the mixture of the oxazoline group-containing polymer and thecompound having a plurality of carboxyl groups, the under coat layer iscrosslinked by a reaction between oxazoline groups of the oxazolinegroup-containing polymer and carboxyl groups of the compound having aplurality of carboxyl groups, thereby the under coat layer to be morefirm, and thus heat resistance and moist heat resistance are improvedand adhesion is enhanced.

The proportion of the compound having a plurality of carboxyl groups is,for example, from 1 to 30 parts by weight, preferably from 2 to 20 partsby weight, and more preferably from 3 to 10 parts by weight, based on100 parts by weight of the total amount of the oxazolinegroup-containing polymer and the compound having a plurality of carboxylgroups. When the amount of the compound having a plurality of carboxylgroups is less than 1 part by weight, the effect of crosslinking theunder coat layer may be lowered. On the other hand, when the amount ofthe compound having a plurality of carboxyl groups is more than 30 partsby weight, the under coat layer becomes opaque and opticalcharacteristics may deteriorate.

Further, in the adhesive optical film of the present invention, undercoat layer is also preferably made of a mixture of an oxazolinegroup-containing polymer, a polyamine-based polymer and a compoundhaving a plurality of carboxyl groups.

The proportion of the polyamine-based polymer is, for example, from 50to 98 parts by weight, preferably from 70 to 97 parts by weight, andmore preferably from 80 to 95 parts by weight, based on 100 parts byweight of the total amount of the oxazoline group-containing polymer,the polyamine-based polymer and the compound having a plurality ofcarboxyl groups. When the polyamine-based polymer is less than 50 partsby weight, moist heat resistance may be inferior. On the other hand,when the amount of the polyamine-based polymer is more than 98 parts byweight, heat resistance may be inferior.

The proportion of the compound having a plurality of carboxyl groups is,for example, from 1 to 30 parts by weight, preferably from 2 to 20 partsby weight, and more preferably from 3 to 10 parts by weight, based on100 parts by weight of the total amount of the oxazolinegroup-containing polymer, the polyamine-based polymer and the compoundhaving a plurality of carboxyl groups. When the amount of the compoundhaving a plurality of carboxyl groups is less than 1 part by weight, theeffect of crosslinking the under coat layer may be lowered. On the otherhand, when the amount of the compound having a plurality of carboxylgroups is more than 30 parts by weight, the under coat layer becomesopaque and optical characteristics may deteriorate.

Such mixture of the oxazoline group-containing polymer, thepolyamine-based polymer and the compound having a plurality of carboxylgroups are generally dissolved or water-dispersed in a solution such asorganic solvent or water, and is prepared as a resin solution or waterdispersion of the mixture of the oxazoline group-containing polymer, thepolyamine-based polymer and the compound having a plurality of carboxylgroups. Preferably, it is prepared as a water dispersible mixture (waterdispersible polymer) of the oxazoline group-containing polymer, thepolyamine-based polymer and the compound having a plurality of carboxylgroups in which the mixture of them is water-dispersed.

The optical film is not specifically limited as far as it is a firmwhich has optical characteristics and is sticked onto a liquid crystaldisplay, and examples thereof include polarizing film, phase differencefilm, luminance improving film and view-angle expansion film.

A polarizing film to be used comprises a polarizer and a transparentprotective film formed on one or both sides of the polarizer.

The polarizer is not specifically limited, and examples thereof includethose obtained by dyeing hydrophilic polymer films such as polyvinylalcohol-based film, partially formalated polyvinyl alcohol-based filmand ethylene-vinyl acetate copolymer-based partially saponified filmwith a dichroic substance such as iodine or dichloric dye, followed bymonoaxial stretching; and polyene-based oriented films subjected to adehydration treatment of polyvinyl alcohol or a dehydrochlorinationtreatment of polyvinyl chloride. A polarizer obtained by dyeing apolyvinyl alcohol-based film with iodine, followed by monoaxialstretching is preferable.

Examples of the transparent protective film include polyester-basedpolymer film such as polyethylene terephthalate or polyethylenenaphthalate, cellulose-based polymer film such as diacetyl cellulose ortriacetyl cellulose, acrylic-based polymer film such as polymethylmethacrylate, styrene-based polymer film such as polystyrene oracrylonitrile-styrene copolymer (AS resin), and polycarbonate-basedpolymer film. The transparent protective film further includespolyolefin-based polymer film such as polyethylene, polypropylene,polyolefin having a cyclo or norbornene structure or ethylene-propylenecopolymer, vinyl chloride-based polymer film, nylon, amide-based polymerfilm such as aromatic polyamide, imide-based polymer film, sulfone-basedpolymer film, polyethersulfone-based polymer film, polyether etherketone-based polymer film, polyphenylene sulfide-based polymer film,vinyl alcohol-based polymer film, vinylidene chloride-based polymerfilm, vinyl butyral-based polymer film, allylate-based polymer film,polyoxymethylene-based polymer film, epoxy-based polymer film, or filmssuch as a blend of the above polymers.

The transparent protective film can be formed as a cured layer made ofan acrylic-based, urethane-based, acryl-urethane-based, epoxy-based orsilicone-based thermosetting or ultraviolet curable resin.

The transparent protective film is preferably made of a cellulose-basedpolymer. The thickness of the transparent protective film is notspecifically limited and is 500 μm or less, preferably from 1 to 300 μm,and more preferably from 5 to 200 μm.

The polarizer is bonded with the transparent protective film using anisocyanate-based adhesive, a polyvinyl alcohol-based adhesive, agelatin-based adhesive, a vinyl-based adhesive, a latex-based adhesiveor water-based polyester adhesive.

Examples of the phase difference film include double refraction filmobtained by monoaxially or diaxially stretching a polymer material,oriented film of a liquid crystal polymer, and film comprising anoriented layer made f a liquid crystal polymer supported thereon. Thethickness of the phase difference film is not specifically limited andis, for example, from 20 to 150 μm.

Examples of the polymer material include polyvinyl alcohol, polyvinylbutyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethylcellulose, hydroxypropyl cellulose, methyl cellulose, polycarbonate,polyallylate, polysulfone, polyethylene terephthalate, polyethylenenaphthalate, polyether sulfone, polyphenylene sulfide, polyphenyleneoxide, polyallyl sulfone, polyvinyl alcohol, polyamide, polyimide,polyolefin, polyvinyl chloride, cellulose-based polymer, or varioustwo-dimensional or three-dimensional copolymers thereof, graftcopolymer, and blends. These polymer materials are formed into anoriented substance (stretched film) by stretching.

Examples of the liquid crystal polymer include various principal chainor side chain type liquid crystal polymers in which a conjugated linearatomic group (mesogen) capable of imparting liquid crystal orientationis introduced into the principal chain or side chain of the polymer. Theprincipal chain type liquid crystal polymer has a structure in which amethogen group is attached at the spacer moiety capable of impartingflexibility, and specific examples thereof include nematically orientedpolyester-based liquid crystal polymer, discotic polymer and cholestericpolymer. Examples of the side chain type liquid crystal polymer includethose which contain polysiloxane, polyacrylate, polymethacrylate orpolymalonate as a principal chain skeleton and also has, as a sidechain, a methogen moiety composed of a para-substituted cyclic compoundunit capable of imparting nematic orientation via a spacer moietycomposed of a conjugated atomic group. These liquid crystal polymers areobtained by spreading a solution of a liquid crystal polymer over anoriented surface such as the surface of a thin film made of polyimide orpolyvinyl alcohol, formed on a glass plate subjected to a rubbingtreatment, or to an oblique deposition with silicon oxide, followed by aheat treatment.

The phase difference film may be one used for the purpose of coloring orfilms having various wavelengths and a liquid crystal layer due todouble refraction or enlarging a view angle, or may appropriately havephase difference according to the purposes, or optical characteristicssuch as phase difference may be controlled by laminating two or morephase difference films.

Examples of the luminance improving film include those which allowpermeation of linear polarization of a predetermined polarizing axis andreflect other light, such as multilayered thin film of dielectrics ormultilayered laminate composed of thin films each having differentrefractive index anisotropy; and those which allow permeation of eitherleft-hand or right-hand circularly polarized light and reflects theother light, such as oriented film of a cholesteric liquid crystalpolymer or a film comprising film base material and an oriented liquidcrystal layer supported on the base material.

The view-angle expansion film is a film used to enlarge a view angle sothat images can be seen comparatively clearly when viewed the imageplane of the liquid crystal display from a slightly diagonal directionrelative to the image plane, not from a perpendicular direction to theimage plane, and examples thereof include phase difference film,oriented film made of liquid crystal polymer, and film comprising atransparent base material supported by an oriented layer such as aliquid crystal polymer. Examples of the phase difference film used asthe view-angle expansion film include polymer film having doublerefraction obtained by biaxially stretched in the plane direction;polymer film having double refraction, in which refractive index in thethickness direction is controlled, obtained by monoaxially stretching inthe plane direction and also under stretch in the thickness direction,and biaxially stretched film such as inclined oriented film.

The adhesive optical film of the present invention includes a thirdadhesive optical film described hereinafter, in addition to the adhesiveoptical films (first and second adhesive optical films).

A method for producing an adhesive optical film of the present inventionwill now be described by way of first, second and third adhesive opticalfilms as examples with reference to FIG. 1 and FIG. 2.

First, an optical film 1 is prepared so as to obtain a first adhesiveoptical film.

As shown in FIG. 1, an adhesive layer 3 made of the water dispersibleadhesive composition of the adhesive composition of the presentinvention is formed on one side of the optical film 1.

The adhesive layer 3 is formed, for example, by a method of transferringthe adhesive layer 3 to the above optical film 1 from a release sheet 4on which the adhesive layer 3 is formed. The release sheet 4 on whichthe adhesive layer 3 is formed is produced by directly coating the waterdispersible adhesive composition on the release sheet 4 using a knowncoating method such as knife coating method, followed by drying. Totransfer the adhesive layer 3, the release sheet 4 on which the adhesivelayer 3 is formed is laminated with the optical film 1 and then therelease sheet 4 is removed from the adhesive layer 3.

The adhesive layer 3 can also be formed, for example, by directlycoating a water dispersible adhesive onto the optical film 1 using aknown coating method such as knife coating method, followed by drying.

As shown in FIG. 2, the optical film 1 may be provided with an undercoat layer 2 so as to improve adhesion (anchoring force) with theadhesive layer 3.

The under coat layer 2 can be formed by appropriately subjecting to aconventional undercoating treatment, previously.

In the first adhesive optical film, there can also be used, as the undercoat layer 2, an under coat layer 2 containing an oxazolinegroup-containing polymer used in the second adhesive optical film(corresponding to a third adhesive optical film described hereinafter inthis case).

Examples of the release sheet 4 include paper; synthetic resin film madeof paper, polyethylene, polypropylene or polyethylene terephthalate;rubber sheet; fabric; nonwoven fabric; net; foamed sheet; metal foil;and laminated sheet material thereof. If necessary, the surface of therelease sheet 4 may be subjected to a treatment such as siliconetreatment, long chain alkyl treatment or fluorine treatment so as toenhance releasability from the adhesive layer 3.

The thickness (thickness after drying) of the adhesive layer 3 is setwithin a range, for example, from 1 to 100 μm, preferably from 5 to 50μm, and more preferably from 10 to 40 μm.

As described above, by forming the adhesive layer 3 made of the waterdispersible adhesive composition on one side of the optical film 1, thefirst adhesive optical film can be obtained.

First, an optical film 1 is prepared so as to obtain a second adhesiveoptical film.

As shown in FIG. 2, an under coat layer 2 is formed on one side of theoptical film 1. In this description, the under coat layer 2 is formed onone side of the optical film and, if necessary, may be formed on bothsides of the optical film.

To form the under coat layer 2, a resin solution or water dispersion ofan oxazoline group-containing polymer, a mixture of an oxazolinegroup-containing polymer and a polyamine-based polymer, a mixture of anoxazoline group-containing polymer and a compound having a plurality ofcarboxyl groups, or a mixture of an oxazoline group-containing polymer,a polyamine-based polymer and a compound having a plurality of carboxylgroups is directly coated onto the optical film 1 using a known coatingmethod such as knife coating method, and then dried.

The thickness (thickness after drying) of the under coat layer 2 is setwithin a range, for example, from 1 to 500 nm, preferably from 10 to 450nm, and more preferably from 20 to 400 nm. When the thickness of theunder coat layer is set within the above range, it is possible tosufficiently increases adhesion between the optical film 1 and theadhesive layer 3.

Then, an adhesive layer 3 is formed on at least one side of the opticalfilm 1 through the under coat layer 2.

The adhesive layer 3 is formed, for example, by the method oftransferring adhesive layer 3 to the above under coat layer 2 from arelease sheet 4 on which the adhesive layer 3 is formed. The releasesheet 4 on which the adhesive layer 3 is formed by directly coating anadhesive onto the release sheet 4 using a known coating method such asknife coating method, followed by drying. To transfer the adhesive layer3, the release sheet 4 on which the adhesive layer 3 is formed islaminated with the optical film 1 on which the under coat layer 2 isformed so as to contact the under coat layer 2 with the adhesive layer3, and then the release sheet 4 is removed from the adhesive layer 3.

The adhesive layer 3 can also be formed, for example, by directlycoating an adhesive onto the under coat layer 2 using a known coatingmethod such as knife coating method, followed by drying.

Examples of the release sheet 4 include the same as those describedabove.

The thickness (thickness after drying) of the adhesive layer 3 is thesame as that described above, and is preferably set within a range from5 to 50 μm, and more preferably from 10 to 40 μm.

As described above, by forming the adhesive layer 3 made of an adhesiveon at least one side of the optical film 1 with the under coat layer 2interposed, a second adhesive optical film can be obtained.

First, an optical film 1 is prepared so as to obtain a third adhesiveoptical film.

An under coat layer 2 is formed on one side of the optical film 1. Inthis description, the under coat layer 2 is formed on one side of theoptical film and, if necessary, the under coat layer is formed on bothsides of the optical film (not shown).

To form the under coat layer 2, a resin solution or water dispersion ofan oxazoline group-containing polymer, or a mixture of an oxazolinegroup-containing polymer and a compound having a plurality of carboxylgroups is directly coated onto the optical film 1 using a known coatingmethod such as knife coating method, and then dried.

The thickness (thickness after drying) of the under coat layer 2 is setwithin a range, for example, from 1 to 500 nm, preferably from 10 to 450nm, and more preferably from 20 to 400 nm. When the thickness of theunder coat layer is set within the above range, it is possible tosufficiently increases adhesion between the optical film 1 and theadhesive layer 3.

Then, an adhesive layer 3 is formed on at least one side of the opticalfilm 1 with the under coat layer 2 interposed.

Examples of the adhesive layer 3 include the same adhesive layer 3 whichis provided on the above first film and is adhesive optical made of awater dispersible adhesive composition of an adhesive composition of thepresent invention.

The adhesive layer 3 is formed, for example, by the method oftransferring adhesive layer 3 to the above under coat layer 2 from arelease sheet 4 on which the adhesive layer 3 is formed. The releasesheet 4, on which the adhesive layer 3 is formed, is produced bydirectly coating a water dispersible adhesive composition of an adhesivecomposition of the present invention onto the release sheet 4 using aknown coating method such as knife coating method, followed by drying.To transfer the adhesive layer 3, the release sheet 4 on which theadhesive layer 3 is formed is laminated with the optical film 1 on whichthe under coat layer 2 is formed so as to contact the under coat layer 2with the adhesive layer 3, and then the release sheet 4 is removed fromthe adhesive layer 3.

The adhesive layer 3 can also be formed, for example, by directlycoating a water dispersible adhesive composition of an adhesivecomposition of the present invention onto the under coat layer 2 using aknown coating method such as knife coating method, followed by drying.

Examples of the release sheet 4 include the same as those describedabove.

The thickness (thickness after drying) of the adhesive layer 3 is thesame as that described above, and is preferably set within a range from5 to 50 μm, and more preferably from 10 to 40 μm.

As described above, by forming an adhesive layer 3 made of the adhesivecomposition of the present invention on at least one side of the opticalfilm 1 with the under coat layer 2 interposed, a third adhesive opticalfilm can be obtained.

The adhesive optical film of the present invention is thus obtainedadvantageously used for various industrial purposes as a polarizingfilm, a phase difference film, a luminance improving film and aview-angle expansion film without deteriorating optical characteristicsof the optical film.

Because of high adhesion between an adhesive layer and an optical film,in case of attaching the adhesive optical film to a liquid crystaldisplay, even if the optical film is once removed from the liquidcrystal display for positioning and then applied again (reworking),reworking can be conducted while effectively suppressing adhesiveresidue on removal. Therefore, efficient applying operation can berealized.

Even if the terminal portion of the adhesive optical film contacts withpersons or articles in the vicinity in case of handling in the step ofcutting or conveying the adhesive optical film, lack of adhesive can beeffectively suppressed. Therefore, poor display of a liquid crystaldisplay caused by lack of adhesive can be effectively prevented.

Further, since such an adhesive optical film has excellent heatresistance, when applied onto a liquid crystal display, decrease inadhesion with the liquid crystal display can be effectively preventedeven in a high temperature atmosphere, and excellent durability can beobtained even in a high temperature atmosphere.

Furthermore, since such an adhesive optical film has excellent moistheat resistance, when applied onto a liquid crystal display, decrease inadhesion with the liquid crystal display can be effectively preventedeven in a high temperature and high humidity atmosphere, and excellentdurability can be obtained even in a high temperature and high humidityatmosphere.

Since the adhesive optical film of the present invention has excellentheat resistance and moist heat resistance, when sticked onto the surfaceof the glass substrate of an image display device, excellent durabilitycan be obtained even in a high temperature atmosphere or a hightemperature and high humidity atmosphere.

Therefore, by sticking the adhesive optical film thus obtained onto thesurface of a glass substrate of image display devices such as a liquidcrystal display, an organic electroluminescence device (organic ELdisplay device) and a plasma display panel (PDP), image display deviceshaving excellent durability can be obtained.

In a conventional water dispersible adhesive composition, a tackifyingresin such as rosin-based resin or elastomer is added so as to enhanceadhesion to an adherend. However, since the water dispersible adhesivecomposition used in the adhesive optical film of the present inventioncan enhance adhesion without adding the tackifying resin, regardless ofwater dispersibility, and thus it is possible to obtain an adhesiveoptical film comprising an adhesive layer made of a water dispersibleadhesive composition, having high adhesion at low cost, and an imagedisplay device comprising such an adhesive optical film.

EXAMPLES

The present invention will now be described in more detail by way ofSynthesis Examples, Examples and Comparative Examples. However, thepresent invention is not limited to the following Synthesis Examples,Examples and Comparative Examples. In the following description, partsand % are by weight standard unless otherwise specified.

Example 1 Preparation of Monomer Preemulsion

In a vessel, 100 parts of butyl acrylate, 5 parts of acrylic acid, 2parts of mono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) and 0.01 parts of3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured bySHIN-ETSU CHEMICAL CO., LTD.) as raw monomers were charged and mixed toprepare a monomer mixture. To 627 g of the monomer mixture thusprepared, 13 g of a reactive emulsifier AQUALON HS-10 (Dai-Ichi KogyoSeiyaku Co., Ltd.) and 360 g of ion-exchange water were added and themixture was forcibly emulsified with stirring at 5000 (1/min) for 5minutes using a homogenizer (manufactured by Tokusyu Kika Kogyo Co.,Ltd.) to prepare a monomer preemulsion.

Preparation of Water Dispersible Adhesive Composition

In a reaction vessel equipped with a condenser tube, a nitrogenintroducing tube, a thermometer and a stirrer, 200 g of the resultingmonomer preemulsion and 330 g of ion-exchange water were charged, andafter replacing the atmosphere in the reaction vessel by nitrogen, 0.2 gof 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropioneamidine]hydrate(VA-057, manufactured by Wako Pure Chemicals Industries, Ltd.) wasadded, followed by polymerization at 60° C. for one hour. Then, 800 g ofthe residual monomer preemulsion was added dropwise in the reactionvessel over 3 hours, followed by polymerization for 3 hours.Furthermore, the polymerization was conducted at 60° C. for 3 hourswhile replacing the atmosphere by nitrogen to obtain an emulsionsolution of a water dispersible adhesive composition having a solidcontent of 48%. After cooling the emulsion solution to room temperature,the pH was adjusted to 8 by adding 10% ammonia water and 3.0 g of anacrylic thickener ARON B-500 (manufactured by Toagosei Co., Ltd.) wasadded to prepare a water dispersible adhesive composition.

Preparation of Optical Film

A polyvinyl alcohol film (thickness: 80 μm) was stretched by 5 times aslong as the original length in an aqueous iodine solution at 40° C.,pulled up from the aqueous iodine solution and then dried at 50° C. for4 minutes to obtain a polarizer. Using a polyvinyl alcohol-basedadhesive, triacetyl cellulose film as a transparent protective film wasbonded to both sides of the polarizer to obtain an optical film.

Preparation of Adhesive Optical Film

The resulting water dispersible adhesive composition was coated onto arelease film (polyethylene terephthalate base material, DIAFOIL MRF38,manufactured by Mitsubishi Polyester Film Corp.), followed by a heattreatment at 100° C. for 2 minutes to form a 23 μm thick adhesive layer.

The adhesive layer thus formed was applied onto the surface of theoptical film subjected previously to an undercoating treatment to obtainan adhesive optical film. The undercoating treatment was conducted bycoating a solution, which was prepared by diluting a mixture (solidcontent: 1:1) of a water dispersible urethane resin (TAKERAK W511,manufactured by MITSUI TAKEDA CHEMICALS, INC.) and a water dispersibleisocyanate-based curing agent (TAKENATE WD725, manufactured by MITSUITAKEDA CHEMICALS, INC.) with a mixed solvent of water and ethanol(weight ratio: 1:1) so as to adjust the solid content to 2% by weight,onto one side of the optical film using a wire bar #5, and drying at 40°C. for 2 minutes.

Example 2

In the same manner as in Example 1, except that 2 parts of themono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) was replaced by 5parts in Example 1, a water dispersible adhesive composition wasprepared and then an adhesive optical film was produced.

Example 3

In the same manner as in Example 1, except that 2 parts of themono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) was replaced by 2parts of a mono[poly(ethylene oxide)methacrylate]phosphate ester(average polymerization degree of ethylene oxide: about 5.5) in Example1, a water dispersible adhesive composition was prepared and then anadhesive optical film was produced.

Example 4

In the same manner as in Example 1, except that 2 parts of themono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) was replaced by 2parts of a mono[poly(propylene oxide)methacrylate]phosphate ester(average polymerization degree of propylene oxide: 5 to 6) in Example 1,a water dispersible adhesive composition was prepared and then anadhesive optical film was produced.

Example 5

In the same manner as in Example 1, except that 5 parts of acrylic acidwas replaced by 11 parts of a β-carboxyethyl acrylate (Sipomer β-CEA,manufactured by Rhodia Nicca, Ltd.) in Example 1, a water dispersibleadhesive composition was prepared and then an adhesive optical film wasproduced.

Example 6

In the same manner as in Example 1, except that 5 parts of acrylic acidwas replaced by 21 parts of a w-carboxy-polycaprolactone monoacrylate(ARONIX M-5300, average polymerization degree of caprolactone group:about 2, manufactured by Toagosei Co., Ltd.) in Example 1, a waterdispersible adhesive composition was prepared and then an adhesiveoptical film was produced.

Comparative Example 1

In the same manner as in Example 1, except that the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was not added in Example 1, a waterdispersible adhesive composition was prepared and then an adhesiveoptical film was produced.

Comparative Example 2

In the same manner as in Example 1, except that 2 parts of themono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) was replaced by 2parts of a mono[2-methacryloyloxyethyl]phosphate ester (polymerizationdegree of oxyethylene group: 1) in Example 1, a water dispersibleadhesive composition was prepared and then an adhesive optical film wasproduced.

Comparative Example 3

In the same manner as in Example 1, except that 2 parts of themono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) was replaced by 2parts of a mono[2-acryloyloxyethyl]phosphate ester (polymerizationdegree of oxyethylene group: 1) in Example 1, a water dispersibleadhesive composition was prepared and then an adhesive optical film wasproduced.

Comparative Example 4

In the same manner as in Example 1, except that acrylic acid was notadded and 2 parts of the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was replaced by 5 parts in Example 1, awater dispersible adhesive composition was prepared and then an adhesiveoptical film was produced.

Comparative Example 5

In the same manner as in Example 1, except that acrylic acid was notadded and 2 parts of the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was replaced by 5 parts of amono[poly(ethylene oxide)methacrylate]phosphate ester (averagepolymerization degree of ethylene oxide: about 5.5) in Example 1, awater dispersible adhesive composition was prepared and then an adhesiveoptical film was produced.

Comparative Example 6

A polymerization was conducted in the same manner as in Example 1,except that, in the preparation of the monomer preemulsion, 5 parts ofacrylic acid was replaced by 20 parts and the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was not added in Example 1. However, sincecohesion occurred during the polymerization, a water dispersibleadhesive composition could not be obtained.

Comparative Example 7

A polymerization was conducted in the same manner as in Example 1,except that, in the preparation of the monomer preemulsion, acrylic acidwas not added and 2 parts of the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was replaced by 25 parts of amono[poly(ethylene oxide)methacrylate]phosphate ester (averagepolymerization degree of ethylene oxide: about 5.5) in Example 1.However, since cohesion occurred during the polymerization, a waterdispersible adhesive composition could not be obtained.

TABLE 1 Average polymerization degree of Composition of raw monomer ofwater oxyalkylene dispersible adhesive composition group Example 1Example 2 Example 3 Example 4 Example 5 Example 6 Alkyl Butyl acrylate —100 100 100 100 100 100 (meth)acrylate ester Carboxyl Acrylic acid — 5 55 5 — — group- β-carboxyethyl acrylate — — — — — 11 — containing(Sipomer β-CEA) vinyl monomer ω-carboxy-polycaprolactone — — — — — — 21monoacrylate (ARONIX M-5300*1) Phosphoric Mono[poly(propylene about 5.02 5 — — 2 2 acid group- oxide)methacrylate]phosphate containing estervinyl monomer Mono[poly(ethylene about 5.5 — — 2 — — —oxide)methacrylate]phosphate ester Mono[poly(propylene 5-6 — — — 2 — —oxide)methacrylate]phosphate ester Mono[2- 1 — — — — — —methacryloyloxyethyl]phosphate ester Mono[2- 1 — — — — — —acryloyloxyethyl]phosphate ester Alkoxysilyl 3-methacryloyloxypropyl- —0.01 0.01 0.01 0.01 0.01 0.01 group- trimethoxysilane containing vinylmonomer Carboxyl group concentration [mmol/g] 0.65 0.63 0.65 0.65 0.680.62 Phosphoric acid group concentration [mmol/g] 0.04 0.10 0.05 0.040.04 0.04 Average polymerization degree of Composition of raw monomer ofwater oxyalkylene Comp. Comp. Comp. Comp. Comp. Comp. Comp. dispersibleadhesive composition group Example 1 Example 2 Example 3 Example 4Example 5 Example 6 Example 7 Alkyl Butyl acrylate — 100 100 100 100 100100 100 (meth)acrylate ester Carboxyl Acrylic acid — 5 5 5 — — 20 —group- β-carboxyethyl acrylate — — — — — — — — containing (Sipomerβ-CEA) vinyl monomer ω-carboxy-polycaprolactone — — — — — — — —monoacrylate (ARONIX M-5300*1) Phosphoric Mono[poly(propylene about 5.0— — — 5 — — — acid group- oxide)methacrylate]phosphate containing estervinyl monomer Mono[poly(ethylene about 5.5 — — — — 5 — 25oxide)methacrylate]phosphate ester Mono[poly(propylene 5-6 — — — — — — —oxide)methacrylate]phosphate ester Mono[2- 1 — 2 — — — — —methacryloyloxyethyl]phosphate ester Mono[2- 1 — — 2 — — — —acryloyloxyethyl]phosphate ester Alkoxysilyl 3-methacryloyloxypropyl- —0.01 0.01 0.01 0.01 0.01 0.01 0.01 group- trimethoxysilane containingvinyl monomer Carboxyl group concentration [mmol/g] 0.66 0.65 0.65 0.000.00 2.31 0.00 Phosphoric acid group concentration [mmol/g] 0.00 0.090.10 0.10 0.12 0.00 0.48 *1Average polymerization degree of caprolactonegroup: about 2

In Table 1, the composition of the monomer is represented by parts byweight. In Table 1, a carboxyl group concentration and a phosphoric acidgroup concentration are also shown.

In Table 1, the carboxyl group concentration was calculated on anassumption that a molecular weight of acrylic acid is 72, a molecularweight of β-carboxyethyl acrylate is 144 and a molecular weight (averagemolecular weight) of a o-carboxy-polycaprolactone monoacrylate (averagepolymerization degree of caprolactone group: about 2) is 276.

In Table 1, the phosphoric acid group concentration was calculated on anassumption that a molecular weight (average molecular weight) of amono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) is 456, a molecularweight (average molecular weight) of a mono[poly(ethyleneoxide)methacrylate]phosphate ester (average polymerization degree ofethylene oxide: about 5.5) is 413.5, a molecular weight (averagemolecular weight) of a mono[poly(propylene oxide)methacrylate]phosphateester (average polymerization degree of propylene oxide: 5 to 6) is 485,a molecular weight (average molecular weight) of amono[2-methacryloyloxyethyl]phosphate ester (polymerization degree ofoxyethylene group: 1) is 210 and a molecular weight (average molecularweight) of a mono[2-acryloyloxyethyl]phosphate ester (polymerizationdegree of oxyethylene group: 1) is 196.

Evaluation

1) Adhesion to Glass

Each of the adhesive optical films of Examples 1 to 6 and ComparativeExamples 1 to 5 was cut into pieces having a width of 25 mm and theresulting cut film was sticked onto a glass plate (Corning #1737,manufactured by Corning Co.), and then they were contact-bonded duringone reciprocation of a rubber roller having a load of 2 kg. Theresulting specimen was allowed to stand in an autoclave at 50° C. under0.5 MPa for 15 minutes and cooled to 25° C., and then a 90° peeladhesion (peel rate: 10 mm/min) was measured (initial adhesion).

The specimen was allowed to stand in the autoclave, allowed to stand inan atmosphere at 60° C. and an atmosphere at 60° C./90° RH for 40 hoursand allowed to stand at 25° C. for one hour, and then a 90° peeladhesion (peel rate: 10 mm/min) was measured. The results are shown inTable 2.

The higher the peel adhesion is, the better adhesion to glass is.

2) Adhesion and Fixation of Adhesive Optical Film

Each of the adhesive optical films of Examples 1 to 6 and ComparativeExamples 1 to 5 was cut into pieces measuring 235 mm×310 mm and theresulting cut film was sticked onto a 0.7 mm thick glass plate (CORNING#1737, manufactured by Corning Co.). The resulting specimen was allowedto stand in an autoclave at 50° C. under 0.5 MPa for 15 minutes, allowedto stand in an atmosphere at 90° C. and an atmosphere at 60° C./90° RHfor 500 hours, and then it was visually observed whether or not peelingof the adhesive optical film occurred. The results are shown in Table 2.

The presence or absence of peeling of the adhesive optical film wasevaluated according to the following criteria.

A: Change such as peeling was not observed.

B: Peeling in size of less than 1 mm was observed at the end of theadhesive optical film.

C: Peeling in size of 1 mm or more was observed at the end of theadhesive optical film.

3) Reworkability

Each of the adhesive optical films of Examples 1 to 6 and ComparativeExamples 1 to 5 was cut into pieces having a width of 25 mm and theresulting cut film was sticked onto a glass plate (CORNING #1737,manufactured by Corning Co.), and then they were contact-bonded by onereciprocation of a rubber roller having a load of 2 kg. The resultingspecimen was allowed to stand in an autoclave at 50° C. under 0.5 MPafor 15 minutes and cooled to 25° C., and then a 90° peel adhesion (peelrate: 300 mm/min) at 50% RH was measured (initial adhesion).

The specimen was allowed to stand in the autoclave, allowed to stand inan atmosphere at 60° C. for 40 hours, cooled to 25° C., and then a 90°peel adhesion (peel rate: 300 mm/min) was measured. The results areshown in Table 2.

The lower the peel adhesion is, the better reworkability is.

4) Gel Fraction

First, each of the water dispersible adhesive composition (about 100 mg)of Examples 1 to 6 and Comparative Examples 1 to 5 was wrapped with aTeflon sheet (trademark, product number: NTF-1122) and a kite string (12cm), weights of which were previously measured, and the weight of theresulting parcel was measured. The parcel was placed in a 50 ml glassbottle and a sufficient amount of ethyl acetate was charged and, aftersealing the glass bottle, the parcel was kept immersed at roomtemperature for 7 days. After pulling up the immersed parcel, ethylacetate adhered to the Teflon sheet was wiped off and the parcel wasdried at 130° C. for 2 hours by a drying machine. Thereafter, the weightof the dried parcel was measured. Then, the gel fraction was calculatedby the following equation.Gel fraction(% by weight)={(C−A)/(B−A)}×100

The symbols in the equation are as follows.

A (g): total weight of a Teflon sheet and a kite string (tare weight)

B (g): total weight of a Teflon sheet, a kite string, and a waterdispersible adhesive composition before being immersed in ethyl acetateand dryed

C (g): total weight of a Teflon sheet, a kite string, and a waterdispersible adhesive composition after being immersed in ethyl acetateand dryed

The measurement results are shown in Table 2.

TABLE 2 Evaluation of physical properties Example 1 Example 2 Example 3Example 4 Example 5 Example 6 Adhesion to Peel Initial 2.5 2.0 2.0 2.42.2 2.0 glass (peel rate [10 mm/min.] at 60° C. for 5.8 6.1 6.1 5.6 5.65.8 adhesion [N/25 mm]) 40 hours at 5.1 9.0 8.9 4.9 5.1 9.0 60° C./90%RH for 40 hours Adhesion and fixation of Heat A A A A A A adhesiveoptical film resistance (90° C.) Moist heat A A A A A A resistance (60°C./90% RH) Reworkability Peel Initial 4.0 3.8 3.2 3.9 3.5 3.1 (peeladhesion rate at 60° C. for 17.8 16.0 14.5 18.3 17.3 11.8 [N/25 mm])[300 mm/min.] 40 hours Gel fraction (%) 91 97 93 89 93 96 Comp. Comp.Comp. Comp. Comp. Comp. Camp. Evaluation of physical properties Example1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Adhesionto Peel Initial 1.0 1.5 1.5 6.5 9.0 Water dispersible glass (peel rate[10 mm/min.] Adhesive Adhesive adhesive adhesion [N/25 mm]) residueresidue composition could at 60° C. for 3.0 3.8 4.0 16.5  16.0  not beobtained 40 hours Adhesive Adhesive because cohesion residue residueoccurred during the at 0.8 2.9 3.2 4.6 7.4 polymerization. 60° C./90% RHAdhesive Adhesive for 40 hours residue residue Adhesion and fixation ofHeat C B B C C adhesive optical film resistance (90° C.) Moist heat B AA C C resistance (60° C./90% RH) Reworkability Peel Initial 2.1 2.1 2.33.4 3.4 (peel adhesion rate at 60° C. for 6.0 10.1 10.8 15.3  17.5 [N/25 mm]) [300 mm/min.] 40 hours Adhesive Adhesive residue residue Gelfraction (%) 89 89 94 95   95  

Synthesis Examples Preparation of Water Dispersible Acrylic Adhesive

In a vessel, 95.2 parts of butyl acrylate, 4.76 parts of acrylic acid,0.02 parts of 3-methacryloxypropyl-trimethoxysilane (KBM-503,manufactured by SHIN-ETSU CHEMICAL CO., LTD.), 2.0 parts (solid content)of a reactive emulsifier AQUALON HS-10 (manufactured by Dai-Ichi KogyoSeiyaku Co., Ltd.) and 57.4 parts of water were charged and then mixedwith stirring at 6000 min⁻¹ for 5 minutes using a homogenizer to preparea monomer emulsion. In another vessel, 0.1 parts of2,2′-azobis[N-(2-carboxyethyl)-2-methylpropioneamidine]hydrate (VA-057,manufactured by Wako Pure Chemicals Industries, Ltd.) was dissolved inwater to prepare an aqueous 10% initiator solution.

In a reaction vessel equipped with a condenser tube, a nitrogenintroducing tube, a thermometer and a stirrer, 52.3 parts of water, a30% amount of the resulting aqueous 10% initiator solution and a 20%amount of the resulting monomer emulsion were charged and thenemulsion-polymerized with stirring at 59° C. for one hour. The entireamount (70% amount) of the residual aqueous 10% initiator solution wasadded and the entire amount (80% amount) of the residual monomeremulsion was added over 3 hours with stirring, and then the mixture wasreacted for 3 hours. After cooling the reaction solution to 30° C. orlower, the pH of the reaction solution was adjusted to 8 by adding 10%ammonia water to obtain a water dispersible acrylic adhesive.

Formation of Adhesive Layer

The water dispersible acrylic adhesive was coated onto a release film(polyethylene terephthalate base material, DIAFOIL MRF38, manufacturedby Mitsubishi Polyester Film Corp.) in a dry thickness of 21 μm and thendried in a hot-air circulating oven at 100° C. for 2 minutes to form anadhesive layer on the release film.

Preparation of Optical Film

A polyvinyl alcohol film (thickness: 80 μm) was stretched by 5 times aslong as the original length in an aqueous iodine solution at 40° C.,pulled up from the aqueous iodine solution and then dried at 50° C. for4 minutes to obtain a polarizer. Using a polyvinyl alcohol-basedadhesive, triacetyl cellulose film as a transparent protective film wasbonded to both sides of the polarizer to obtain an optical film.

Example 7

EPOCROS WS-700 (oxazoline group-containing acrylic polymer, manufacturedby Nippon Shokubai Co., Ltd.) was diluted with a solution mixture ofwater and ethanol (volume ratio: 1:1) to prepare an undercoating agentsolution having a solid content of 2%. This undercoating agent solutionwas coated onto one side of an optical film using a mayer bar #5 andthen dried at 40° C. for 2 minutes to form an under coat layer. Then, arelease film formed with an adhesive layer was laminated on one side ofthe optical film provided with the under coat layer to produce anadhesive optical film.

Example 8

In the same manner as in Example 7, except that EPOCROS WS-700(oxazoline group-containing acrylic polymer, manufactured by NipponShokubai Co., Ltd.) used to prepare the undercoating agent solution wasreplaced by EPOCROS WS-500 (oxazoline group-containing acrylic polymer,manufactured by Nippon Shokubai Co., Ltd.), an adhesive optical film wasproduced.

Example 9

In the same manner as in Example 7, except that the solid content of 2%of the undercoating agent solution was replaced by 5%, an adhesiveoptical film was produced.

Example 10

In the same manner as in Example 7, except that, in the preparation ofthe undercoating agent solution of Example 7, EPOCROS WS-700 (oxazolinegroup-containing acrylic polymer, manufactured by Nippon Shokubai Co.,Ltd.) used to prepare the undercoating agent solution was replaced by amixtured solution mixture (mixing ratio is 5:95 in terms of a solidcontent ratio) of EPOCROS WS-700 (oxazoline group-containing acrylicpolymer, manufactured by Nippon Shokubai Co., Ltd.) and POLYMENT SK-1000(ethyleneimine-modified acrylic polymer, manufactured by Nippon ShokubaiCo., Ltd.), and the mixtured solution mixture of water and ethanol(volume ratio: 1:1) was replaced by water, an undercoating agentsolution was prepared and an adhesive optical film was produced.

Example 11

In the same manner as in Example 7, except that, in the preparation ofthe undercoating agent solution of Example 7, EPOCROS WS-700 (oxazolinegroup-containing acrylic polymer, manufactured by Nippon Shokubai Co.,Ltd.) used to prepare the undercoating agent solution was replaced by amixtured solution (mixing ratio is 95:5 in terms of a solid contentratio) of EPOCROS WS-700 (oxazoline group-containing acrylic polymer,manufactured by Nippon Shokubai Co., Ltd.) and POISE 532A (acrylicacid-maleic acid copolymer ammonium salt, number average molecularweight: about 10000, manufactured by Kao Corporation), and the mixturedsolution of water and ethanol (volume ratio: 1:1) was replaced by water,an undercoating agent solution was prepared and an adhesive optical filmwas produced.

Example 12

In the same manner as in Example 7, except that, in the preparation ofthe undercoating agent solution of Example 7, EPOCROS WS-700 (oxazolinegroup-containing acrylic polymer, manufactured by Nippon Shokubai Co.,Ltd.) used to prepare the undercoating agent solution was replaced by amixtured solution(mixing ratio is 5:90:5 in terms of a solid contentratio) of EPOCROS WS-700 (oxazoline group-containing acrylic polymer,manufactured by Nippon Shokubai Co., Ltd.), POLYMENT SK-1000(ethyleneimine-modified acrylic polymer, manufactured by Nippon ShokubaiCo., Ltd.) and POISE 532A (acrylic acid-maleic acid copolymer ammoniumsalt, number average molecular weight: about 10000, manufactured by KaoCorporation), and the mixtured solution of water and ethanol (volumeratio: 1:1) was replaced by water, an undercoating agent solution wasprepared and an adhesive optical film was produced.

Example 13

In the same manner as in Example 7, except that the solid content of 2%of the undercoating agent solution was replaced by 0.25%, adhesiveoptical film was produced.

Comparative Example 8

In the same manner as in Example 7, except that EPOCROS WS-700(oxazoline group-containing acrylic polymer, manufactured by NipponShokubai Co., Ltd.) used to prepare the undercoating agent solution wasreplaced by a water dispersible urethane resin TAKERAK W-511 (MITSUITAKEDA CHEMICALS, INC.), an adhesive optical film was produced.

Comparative Example 9

In the same manner as in Example 7, except that EPOCROS WS-700(oxazoline group-containing acrylic polymer, manufactured by NipponShokubai Co., Ltd.) used to prepare the undercoating agent solution wasreplaced by a water dispersible polyester-based resin VYLON TAD-1000(manufactured by Toyobo., Ltd.), an adhesive optical film was produced.

Comparative Example 10

In the same manner as in Example 7, except that EPOCROS WS-700(oxazoline group-containing acrylic polymer, manufactured by NipponShokubai Co., Ltd.) used to prepare the undercoating agent solution wasreplaced by a water dispersible vinyl acetate-based resin BONCOAT 9180(Manufactured by DAINIPPON INK AND CHEMICALS, INC.), an adhesive opticalfilm was produced.

Comparative Example 11

In the same manner as in Example 7, except that EPOCROS WS-700(oxazoline group-containing acrylic polymer, manufactured by NipponShokubai Co., Ltd.) used to prepare the undercoating agent solution wasreplaced by a carbodiimide group-containing water dispersible acrylicresin CARBODILITE E-01 (manufactured by Nisshinbo Industries, Inc.), anadhesive optical film was produced.

Comparative Example 12

In the same manner as in Example 7, except that, in the preparation ofthe undercoating agent solution of Example 7, EPOCROS WS-700 (oxazolinegroup-containing acrylic polymer, manufactured by Nippon Shokubai Co.,Ltd.) used to prepare the undercoating agent solution was replaced byPOLYMENT SK-1000 (ethyleneimine-modified acrylic polymer, manufacturedby Nippon Shokubai Co., Ltd.), and the mixtured solution of water andethanol (volume ratio: 1:1) was replaced by water, an undercoating agentsolution was prepared and an adhesive optical film was produced.

Comparative Example 13

In the same manner as in Example 7, except that the under coat layer wasnot formed, an adhesive optical film was produced.

Evaluation

5) Thickness of Under Coat Layer

In Examples 7 to 13 and Comparative Examples 8 to 13, each adhesiveoptical film provided with only an under coat layer was stained with anaqueous 2% ruthenic acid solution for 2 minutes, embedded in an epoxyresin and then the epoxy resin was cut into pieces having a thickness ofabout 80 nm using an ultramicrotome (Ultracut S, manufactured by LeicaCo.). Then, the thickness of the under coat layer was determined byobserving a cross section of a slice of the optical film by TEM (HitachiH-7650, acceleration voltage: 100 kV). The results are shown in Table 3.

6) Haze

In Examples 7 to 13 and Comparative Examples 8 to 13, each optical filmprovided with only an under coat layer (that is, adhesive optical filmbefore forming an adhesive layer) was cut into pieces measuring 50 mm×50mm and haze was measured by a haze computer HZ-1 (Suga Test InstrumentsCo., Ltd.). The results are shown in Table 3. Usually, the haze ispreferably 2.0 or less. When the haze exceeds 2%, the optical film giveswhite appearance due to visual observation, and this is not preferable.

7) Adhesion Between Adhesive Layer and Optical film

Each of the adhesive optical films of Examples 7 to 13 and ComparativeExamples 8 to 13 was cut into pieces measuring 25 mm×120 mm to obtain asample. This sample was aged in an atmosphere at 23° C./60% RH, anatmosphere at 50° C. and an atmosphere at 60° C./90% RH for one day,respectively. After aging, a release film was removed and apolypropylene porous membrane was applied onto the adhesive surface ofthe sample and an adhesive tape (No. 31B, manufactured by Nitto DenkoCorporation) was sticked onto the polypropylene porous membrane, toreinforce the sample. Then, the sample was allowed to stand in anatmosphere at 23° C./60% RH for 24 hours. Using a double-faced tape, aSUS304 steel plate was attached onto the back surface of the adhesiveoptical film after standing. Using a tensile testing machine, thepolypropylene porous membrane and the adhesive tape (No. 31B) wereremoved in a 180° direction at a rate of 300 mm/min. After confirmingthat the adhesive layer adheres to the side of the polypropylene porousmembrane, a peel stress was measured. The results are shown in Table 3.Usually, the adhesion was preferably 5.0 N/25 mm or more.

8) Heat Resistance

Each of the adhesive optical films of Examples 7 to 13 and ComparativeExamples 8 to 13 was cut into pieces measuring 230 mm×310 mm to obtain asample. This sample was sticked onto a glass plate (thickness: 0.7 mm,CORNING #1737, manufactured by Corning Co.) at the adhesive surface andthen allowed to stand in an atmosphere at 50° C. at 0.5 MPa for 15minutes. This sample was stored at 90° C. for 500 hours and it wasvisually observed whether or not peeling of the adhesive optical filmoccurred. The results are shown in Table 3.

In Table 3, the symbol “A” indicates that defects such as lifting andpeeling are not observed, “B” indicates that peeling in size of lessthan 1 mm is observed, and “C” indicates that peeling in size of 1 mm ormore is observed

9) Moist Heat Resistance

Each of the adhesive optical films of Examples 7 to 13 and ComparativeExamples 8 to 13 was cut into pieces measuring 230 mm×310 mm to obtain asample. This sample was sticked onto a glass plate (thickness: 0.7 mm,CORNING #1737, manufactured by Corning Co.) at the adhesive surface andthen allowed to stand in an atmosphere at 50° C. at 0.5 MPa for 15minutes. This sample was stored at 60° C./90% RH for 500 hours and itwas visually observed whether or not peeling of the adhesive opticalfilm occurred. The results are shown in Table 3.

In Table 3, the symbol “A” indicates that defects such as lifting andpeeling are not observed, “B” indicates that peeling in size of lessthan 1 mm is observed, and “C” indicates that peeling in size of 1 mm ormore is observed.

TABLE 3 Example Example Example Example Example 7 Example 8 Example 9 1011 12 13 Undercoat layer 175 175 285 175 175 175 50 Thickness [nm] Haze[%] 0.6 0.5 0.6 0.6 0.8 0.8 0.6 Adhesion [N/25 mm] 23° C./60% RH 9.710.0 8.7 11.3 11.7 10.5 9.6 50° C. 16.0 17.3 15.4 16.0 20.0 17.5 15.860° C./90% RH 2.0 1.1 0.5 15.0 15.1 10.2 8.8 Heat resistance 90° C. A AA A A A A Moist heat resistance 60° C./90% RH C C C A C C C Comp. Comp.Comp. Comp. Comp. Comp. Example 8 Example 9 Example 10 Example 11Example 12 Example 13 Undercoat layer 175 175 175 175 175 — Thickness[nm] Haze [%] 0.4 0.5 22.3 6.9 0.6 0.5 Adhesion [N/25 mm] 23° C./60% RH9.1 6.8 1.6 4.1 11.6 3.6 50° C. 10.1 7.0 2.1 4.8 11.0 3.2 60° C./90% RH8.5 4.6 1.0 2.2 10.3 2.5 Heat resistance 90° C. C C C C B C Moist heatresistance 60° C./90% RH B C C C B C

As is apparent from the results shown in Table 3, the adhesive opticalfilms of Examples 7 to 13 can attain high adhesion between the adhesivelayer and the optical film and can attain high adhesion even when agedby heating as compared with the adhesive optical film provided with nounder coat layer of Comparative Example 13 and the adhesive opticalfilms provided with the other under coat layer of Comparative Examples 8to 12. Also the adhesive optical films of the Examples 7 to 13 areexcellent in heat resistance. The adhesive optical film of Example 10 inwhich an oxazoline group-containing acryl polymer is used in combinationwith a polyamine-based polymer in an under coat layer is excellent inmoist heat resistance as compared with the adhesive optical films ofExamples 7 to 9 in which an oxazoline group-containing acryl polymer isused alone. The adhesive optical film of Comparative Example 12 in whicha polyamine-based polymer is used alone is a little excellent in bothheat resistance and moist heat resistance as compared with the adhesiveoptical films of Comparative Examples 8 to 11 and 13. The adhesiveoptical film of Example 10 in which an oxazoline group-containing acrylpolymer is used in combination is excellent in not only heat resistancebut also moist heat resistance.

When comparing a thin under coat layer of Example 13 with a thick undercoat layer of Examples 7 to 9, the adhesion decreases due to aging withheating and humidifying when the thickness of the under coat layerincreases, and the adhesion does not decrease when the under coat layeris thin.

When comparing the adhesive optical films of Examples 11 and 12 in whichan oxazoline group-containing acryl polymer is used in combination witha compound having a plurality of carboxyl groups in an under coat layerwith the adhesive optical films of Examples 7 to 9 in which an oxazolinegroup-containing acryl polymer is used alone, the adhesion does notdecrease even when the under coat layer is thick and the adhesionincreases particularly due to aging with heating and humidifying.

Example 14 Preparation of Monomer Preemulsion

In a vessel, 100 parts of butyl acrylate, 5 parts of acrylic acid, 2parts of mono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) and 0.01 parts of3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured bySHIN-ETSU CHEMICAL CO., LTD.) as raw monomers were charged and mixed toprepare a monomer mixture. To 627 g of the monomer mixture thusprepared, 13 g (2 parts (solid content)) of AQUALON HS-10 (Dai-IchiKogyo Seiyaku Co., Ltd.) as an emulsifier and 360 g of ion-exchangewater were added and the mixture was forcibly emulsified with stirringat 5000 (1/min) for 5 minutes using a homogenizer (manufactured byTokusyu Kika Kogyo Co., Ltd.) to prepare a monomer preemulsion.

Preparation of Water Dispersible Adhesive Composition

In a reaction vessel equipped with a condenser tube, a nitrogenintroducing tube, a thermometer and a stirrer, 200 g of the resultingmonomer preemulsion and 330 g of ion-exchange water were charged, andafter replacing the atmosphere in the reaction vessel by nitrogen, 0.2 gof 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropioneamidine]hydrate(VA-057, manufactured by Wako Pure Chemicals Industries, Ltd.) wasadded, followed by polymerization at 60° C. for one hour. Then, 800 g ofthe residual monomer preemulsion was added dropwise in the reactionvessel over 3 hours, followed by polymerization for 3 hours.Furthermore, the polymerization was conducted at 60° C. for 3 hourswhile replacing the atmosphere by nitrogen to obtain an emulsionsolution of a water dispersible adhesive composition having a solidcontent of 48%. After cooling the emulsion solution to room temperature,the pH was adjusted to 8 by adding 10% ammonia water and 3.0 g of anacrylic thickener ARON B-500 (manufactured by Toagosei Co., Ltd.) wasadded to prepare a water dispersible adhesive composition.

Preparation of Optical Film

A polyvinyl alcohol film (thickness: 80 μm) was stretched by 5 times aslong as the original length in an aqueous iodine solution at 40° C.,pulled up from the aqueous iodine solution and then dried at 50° C. for4 minutes to obtain a polarizer. Using a polyvinyl alcohol-basedadhesive, triacetyl cellulose film as a transparent protective film wasbonded to both sides of the polarizer to obtain an optical film.

Undercoating Treatment

An undercoating treatment was conducted by coating a solution, which wasprepared by diluting EPOCROS WS-500 (oxazoline group-containing acrylicpolymer, manufactured by Nippon Shokubai Co., Ltd.) with a mixturedsolution of water and ethanol (weight ratio: 1:1) so as to adjust thesolid content to 0.25% by weight, onto one side of the optical filmusing a wire bar #5, and drying at 40° C. for 2 minutes.

Preparation of Adhesive Optical Film

The resulting water dispersible adhesive composition was coated onto arelease film (polyethylene terephthalate base material, DIAFOIL MRF38,manufactured by Mitsubishi Polyester Film Corp.), followed by a heattreatment at 100° C. for 2 minutes to form a 23 μm thick adhesive layer.The resulting adhesive layer was attached to a surface of an opticalfilm which was preliminarily undercoated to obtain an adhesive opticalfilm.

Example 15

In the same manner as in Example 14, except that, in the undercoatingtreatment of Example 14, EPOCROS WS-500 (oxazoline group-containingacrylic polymer, manufactured by Nippon Shokubai Co., Ltd.) was replacedby WS-700 (oxazoline group-containing acrylic polymer, manufactured byNippon Shokubai Co., Ltd.), an adhesive optical film was produced.

Example 16

In the same manner as in Example 14, except that, in the monomerpreemulsion of Example 14, 0.01 parts of3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured bySHIN-ETSU CHEMICAL CO., LTD.) was replaced by 0.02 parts of3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured bySHIN-ETSU CHEMICAL CO., LTD.), 13 g (2 parts (solid content)) of AQUALONHS-10 (manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.) as anemulsifier was replaced by 19 g (3 parts (solid content)) of AQUALONHS-10 (manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.), and 360 g ofion-exchange water was replaced by 354 g of ion-exchange water, amonomer preemulsion was prepared. Subsequently, a water dispersibleadhesive composition was prepared in the same manner as in Example 14.

In the same manner as in Example 14, except that, in the preparation ofthe undercoating agent solution in the undercoating treatment of Example14, EPOCROS WS-500 (oxazoline group-containing acrylic polymer,manufactured by Nippon Shokubai Co., Ltd.) used to prepare theundercoating agent solution was replaced by a mixtured solution(mixingratio is 95:5 in terms of a solid content ratio) of EPOCROS WS-700(oxazoline group-containing acrylic polymer, manufactured by NipponShokubai Co., Ltd.) and POISE 532A (acrylic acid-maleic acid copolymerammonium salt, number average molecular weight: about 10000,manufactured by Kao Corporation) and solid content of 0.25% by weight ofthe undercoating agent solution was replaced by 2.0% by weight, anundercoating agent solution was prepared and an adhesive optical filmwas produced.

Example 17

In the same manner as in Example 14, except that, in the monomerpreemulsion of Example 14, 2 parts of the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was replaced by 3 parts of amono[poly(propylene oxide) methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) and 13 g (2 parts(solid content)) of AQUALON HS-10 (manufactured by Dai-Ichi KogyoSeiyaku Co., Ltd.) as an emulsifier was replaced by 13 g (2 parts (solidcontent)) of HITENOL LA-16 (manufactured by Dai-Ichi Kogyo Seiyaku Co.,Ltd.), a monomer preemulsion was prepared. Subsequently, a waterdispersible adhesive composition was prepared in the same manner as inExample 14.

Then, an adhesive optical film was produced in the same manner as inExample 15.

Example 18

In the same manner as in Example 14, except that, in the monomerpreemulsion of Example 14, 2 parts of the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was replaced by 4 parts of amono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0), 13 g (2 parts(solid content)) of AQUALON HS-10 (manufactured by Dai-Ichi KogyoSeiyaku Co., Ltd.) as an emulsifier was replaced by 19 g (3 parts (solidcontent)) of HITENOL LA-16 (manufactured by Dai-Ichi Kogyo Seiyaku Co.,Ltd.) and 360 g of ion-exchange water was replaced by 354 g ofion-exchange water, a monomer preemulsion was prepared. Subsequently, awater dispersible adhesive composition was prepared in the same manneras in Example 14.

Then, an adhesive optical film was produced in the same manner as inExample 15.

Example 19

In the same manner as in Example 18, a monomer preemulsion was preparedand a water dispersible adhesive composition was prepared.

In the same manner as in Example 14, except that, in the preparation ofthe undercoating agent solution in the undercoating treatment of Example14, EPOCROS WS-500 (oxazoline group-containing acrylic polymer,manufactured by Nippon Shokubai Co., Ltd.) used to prepare theundercoating agent solution was replaced by WS-700 (oxazolinegroup-containing acrylic polymer, manufactured by Nippon Shokubai Co.,Ltd.), and the solid content of 0.25% by weight of the undercoatingagent solution was replaced by 0.1% by weight, an adhesive optical filmwas produced.

Example 20

In the same manner as in Example 18, a monomer preemulsion was preparedand a water dispersible adhesive composition was prepared.

In the same manner as in Example 14, except that, in the preparation ofthe undercoating agent solution in the undercoating treatment of Example14, EPOCROS WS-500 (oxazoline group-containing acrylic polymer,manufactured by Nippon Shokubai Co., Ltd.) used to prepare theundercoating agent solution was replaced by WS-700 (oxazolinegroup-containing acrylic polymer, manufactured by Nippon Shokubai Co.,Ltd.), and the solid content of 0.25% by weight of the undercoatingagent solution was replaced by 0.5% by weight, an adhesive optical filmwas produced.

Example 21

In the same manner as in Example 14, except that, in the monomerpreemulsion of Example 14, 5 parts of acrylic acid was replaced by 11parts of β-carboxyethyl acrylate (Sipomer β-CEA, manufactured by RhodiaNicca, Ltd.) and 2 parts of the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was replaced by the 4 parts ofmono[poly(propylene oxide) methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0), a monomerpreemulsion was prepared. Subsequently, a water dispersible adhesivecomposition was prepared in the same manner as in Example 14.

Then, an adhesive optical film was produced in the same manner as inExample 15.

Example 22

In the same manner as in Example 14, except that, in the monomerpreemulsion of Example 14, 5 parts of acrylic acid was replaced by 0.5parts of acrylic acid and 18.8 parts of ω-carboxy-polycaprolactonemonoacrylate (ARONIX M-5300, average polymerization degree ofcaprolactone group: about 2, manufactured by Toagosei Co., Ltd.), 2parts of the mono[poly(propylene oxide)methacrylate]phosphate ester(average polymerization degree of propylene oxide: about 5.0) wasreplaced by 4 parts of a mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) and 13 g (2 parts (solid content)) ofAQUALON HS-10 (manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.) as anemulsifier was replaced by 19 g (3 parts (solid content)) of HITENOLLA-16 (manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.), a monomerpreemulsion was prepared. Subsequently, a water dispersible adhesivecomposition was prepared in the same manner as in Example 14.

Then, an adhesive optical film was produced in the same manner as inExample 15.

Comparative Example 14

In the same manner as in Example 14, except that, in the monomerpreemulsion of Example 14, the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was not added and 0.01 parts of3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured bySHIN-ETSU CHEMICAL CO., LTD.) was replaced by 0.06 parts of3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured bySHIN-ETSU CHEMICAL CO., LTD.), a monomer preemulsion was prepared.Subsequently, a water dispersible adhesive composition was prepared inthe same manner as in Example 14.

Then, an adhesive optical film was produced in the same manner as inExample 15.

Comparative Example 15

In the same manner as in Example 14, a monomer preemulsion was preparedand a water dispersible adhesive composition was prepared.

In the same manner as in Example 14, except that, in the preparation ofthe undercoating agent solution in the undercoating treatment of Example14, EPOCROS WS-500 (oxazoline group-containing acrylic polymer,manufactured by Nippon Shokubai Co., Ltd.) used to prepare theundercoating agent solution was replaced by a mixtured solution(mixingratio is 1:1 in terms of a solid content ratio) of a water dispersibleurethane resin (TAKERAK W511, manufactured by MITSUI TAKEDA CHEMICALS,INC.) and a water dispersible isocyanate-based curing agent (TAKENATEWD725, manufactured by MITSUI TAKEDA CHEMICALS, INC.), and the solidcontent of 0.25% by weight of the undercoating agent solution wasreplaced by 2.0% by weight, an undercoating agent solution was preparedand an adhesive optical film was produced.

Comparative Example 16

In the same manner as in Example 14, except that, in the monomerpreemulsion of Example 14, the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was not added and 0.01 parts of3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured bySHIN-ETSU CHEMICAL CO., LTD.) was replaced by 0.02 parts of3-methacryloyloxypropyl-trimethoxysilane (KBM-503, manufactured bySHIN-ETSU CHEMICAL CO., LTD.), a monomer preemulsion was prepared.Subsequently, a water dispersible adhesive composition was prepared inthe same manner as in Example 14.

In the same manner as in Example 14, except that, in the preparation ofthe undercoating agent solution in the undercoating treatment of Example14, EPOCROS WS-500 (oxazoline group-containing acrylic polymer,manufactured by Nippon Shokubai Co., Ltd.) used to prepare theundercoating agent solution was replaced by POLYMENT SK-1000(ethyleneimine-modified acrylic polymer, manufactured by Nippon ShokubaiCo., Ltd.), and the solid content of 0.25% by weight of the undercoatingagent solution was replaced by 2.0% by weight, an adhesive optical filmwas produced.

Comparative Example 17

In the same manner as in Example 14, except that, in the monomerpreemulsion of Example 14, 5 parts of acrylic acid was replaced by 20parts of acrylic acid and the mono[poly(propyleneoxide)methacrylate]phosphate ester (average polymerization degree ofpropylene oxide: about 5.0) was not added, a monomer preemulsion wasprepared. Subsequently, the polymerization was conducted in the samemanner as in Example 14. However, since cohesion occurred during thepolymerization, a water dispersible adhesive composition could not beobtained.

Comparative Example 18

In the same manner as in Example 14, except that, in the monomerpreemulsion of Example 14, acrylic acid was not added and 2 parts of themono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) was replaced by 25parts of a mono[poly(ethylene oxide)methacrylate]phosphate ester(average polymerization degree of ethylene oxide: about 5.5), a monomerpreemulsion was prepared. Subsequently, the polymerization was conductedin the same manner as in Example 14. However, since cohesion occurredduring the polymerization, a water dispersible adhesive compositioncould not be obtained.

TABLE 4 Example Example Example Example Example Composition of rawmaterial (monomer) 14 15 16 17 18 Example 19 Example 20 Water AlkylButyl acrylate 100 100 100 100 100 100 100 dispersible (meth)acrylateadhesive ester composition Carboxyl Acrylic acid 5 5 5 5 5 5 5 (adhesivegroup- β-carboxyethyl acrylate — — — — — — — layer) containing (Sipomerβ-CEA) vinyl monomer ω-carboxy-polycaprolactone — — — — — — —monoacrylate (ARONIX M-5300*2) Phosphoric Mono[poly(propylene 2 2 2 3 44 4 acid group- oxide)methacrylate]phosphate containing ester*3 vinylmonomer Mono[poly(ethylene — — — — — — — oxide)methacrylate]phosphateester*4 Alkoxysilyl 3-methacryloyloxypropyl- 0.01 0.01 0.02 0.01 0.010.01 0.01 group- trimethoxysilane containing vinyl monomer EmulsifierAQUALON HS-10 2 2 3 — — — — HITENOL LA-16 — — — 2 3 3 3 LATEMUL PD-104 —— — — — — — Comp. Comp. Comp. Comp. Comp. Example Example ExampleExample Example Example Example Composition of raw material (monomer) 2122 14 15 16 17 18 Water Alkyl Butyl acrylate 100 100 100 100 100 100 100dispersible (meth)acrylate adhesive ester composition Carboxyl Acrylicacid — 0.5 5 5 5 20 — (adhesive group- β-carboxyethyl acrylate 11 — — —— — — layer) containing (Sipomer β-CEA) vinyl monomerω-carboxy-polycaprolactone — 18.8 — — — — — monoacrylate (ARONIXM-5300*2) Phosphoric Mono[poly(propylene 4 4 — — — — — acid group-oxide)methacrylate]phosphate containing ester*3 vinyl monomerMono[poly(ethylene — — — — — — 25 oxide)methacrylate]phosphate ester*4Alkoxysilyl 3-methacryloyloxypropyl- 0.01 0.01 0.06 0.06 0.02 0.01 0.01group- trimethoxysilane containing vinyl monomer Emulsifier AQUALONHS-10 2 — 2 2 2 2 2 HITENOL LA-16 — 3 — — — — — LATEMUL PD-104 — — — — —— — Composition of raw material Example Example Example Example ExampleExample Example (monomer) 14 15 16 17 18 19 20 Undercoating Oxazolinegroup- EPOCROS 0.25 — — — — — — agent containing polymer WS-500 solutionEPOCROS — 0.25 — 0.25 0.25 0.1  0.5  (undercoat WS-700 layer)*1 Mixtureof oxazoline EPOCROS — — 2   — — — — group-containing polymer WS-700/(95/5) and carboxyl group- POISE containing compound 532A Oxazolinegroup-free TAKERAK — — — — — — — polymer W511/ TAKENATE WD725 POLYMENT —— — — — — — SK-1000 Carboxyl group concentration [mmol/g] 0.65 0.65 0.650.64 0.64 0.64 0.64 Phosphoric acid group concentration [mmol/g] 0.040.04 0.04 0.06 0.08 0.08 0.08 Comp. Comp. Comp. Comp. Comp. Compositionof raw material Example Example Example Example Example Example Example(monomer) 21 22 14 15 16 17 18 Undercoating Oxazoline group- EPOCROS — —— — — agent containing polymer WS-500 solution EPOCROS 0.25 0.25 0.25 —— (undercoat WS-700 layer)*1 Mixture of oxazoline EPOCROS — — — — —group-containing polymer WS-700/ and carboxyl group- POISE containingcompound 532A Oxazoline group-free TAKERAK — — — 2 (1/1) — polymer W511/TAKENATE WD725 POLYMENT — — — — 2   SK-1000 Carboxyl group concentration[mmol/g] 0.66 0.61 0.66 0.66 0.66 2.31 0.00 Phosphoric acid groupconcentration [mmol/g] 0.08 0.07 0.00 0.00 0.00 0.00 0.48 *1Thenumerical value indicates a solid content (% by weight) in anundercoating agent solution. The numerical value in parenthesisindicates a solid content ratio. *2Average polymerization degree ofcaprolactone group: about 2 *3Average polymerization degree of propyleneoxide: about 5.0 *4Average polymerization degree of ethylene oxide:about 5.5

In Table 4, the composition of the monomer is represented by parts byweight. In Table 4, a carboxyl group concentration and a phosphoric acidgroup concentration are also shown.

In Table 4, the carboxyl group concentration was calculated on theassumption that a molecular weight of acrylic acid is 72, a molecularweight of a β-carboxyethyl acrylate is 144 and a molecular weight(average molecular weight) of a w-carboxy-polycaprolactone monoacrylate(average polymerization degree of caprolactone group: about 2) is 276.

In Table 4, the phosphoric acid group concentration was calculated onthe assumption that a molecular weight (average molecular weight) of amono[poly(propylene oxide)methacrylate]phosphate ester (averagepolymerization degree of propylene oxide: about 5.0) is 456 and amolecular weight (average molecular weight) of a mono[poly(ethyleneoxide)methacrylate]phosphate ester (average polymerization degree ofethylene oxide: about 5.5) is 413.5.

The numerical value in the column of an undercoating agent solution(under coat layer) in Table 4 indicates a solid content (% by weight) inan undercoating agent solution. The numerical value in parenthesisindicates a solid content ratio.

Evaluation

10) Adhesion to Glass of Adhesive Optical Film

Each of the adhesive optical films of Examples 14 to 22 and ComparativeExamples 14 to 16 was cut into pieces having a width of 25 mm and theresulting cut film was sticked onto a glass plate (CORNING #1737,manufactured by Corning Co.), and then they were contact-bonded duringone reciprocation of a rubber roller having a load of 2 kg. Theresulting specimen was allowed to stand in an autoclave at 50° C. under0.5 MPa for 15 minutes and cooled to 25° C., and then a 90° peeladhesion (peel rate: 300 mm/min) was measured (initial adhesion).

The specimen was allowed to stand in the autoclave, allowed to stand inan atmosphere at 60° C. for 40 hours and cooled to 25° C., and then a90° peel adhesion (peel rate: 300 mm/min) was measured. The results areshown in Table 5.

The higher the peel adhesion is, the better adhesion to glass is.

11) Adhesion and Fixation of Adhesive Optical film

Each of the adhesive optical films of Examples 14 to 22 and ComparativeExamples 14 to 16 was cut into pieces measuring 235 mm×310 mm and theresulting cut film was sticked onto a 0.7 mm thick glass plate (CORNING#1737, manufactured by Corning Co.). The resulting specimen was allowedto stand in an autoclave at 50° C. under 0.5 MPa for 15 minutes, allowedto stand in an atmosphere at 90° C. and an atmosphere at 60° C./90° RHfor 500 hours, and then it was visually observed whether or not peelingof the adhesive optical film occurred. The results are shown in Table 5.

The presence or absence of peeling of the adhesive optical film wasevaluated according to the following criteria.

A: Change such as peeling was not observed.

B: Peeling in size of less than 1 mm was observed at the end of theadhesive optical film.

C: Peeling in size of 1 mm or more was observed at the end of theadhesive optical film.

12) Gel Fraction of Water Dispersible Adhesive Composition

First, each of the water dispersible adhesive composition (about 100 mg)of Examples 14 to 22 and Comparative Examples 14 to 16 was wrapped witha Teflon sheet (trademark, product number: NTF-1122) and a kite string(12 cm), weights of which were previously measured, and the weight ofthe resulting parcel was measured. The parcel was placed in a 50 mlglass bottle and a sufficient amount of ethyl acetate was charged and,after sealing the glass bottle, the parcel was kept immersed at roomtemperature for 7 days. After pulling up the immersed parcel, ethylacetate adhered to the Teflon sheet was wiped off and the parcel wasdried at 130° C. for 2 hours by a drying machine. Thereafter, the weightof the dried parcel was measured. Then, the gel fraction was calculatedby the following equation.Gel fraction(% by weight)={(C−A)/(B−A)}×100

The symbols in the equation are as follows.

A (g): total weight of a Teflon sheet and a kite string (tare weight)

B (g): total weight of a Teflon sheet, a kite string and a waterdispersible adhesive composition before being immersed in ethyl acetateand dryed

C (g): total weight of a Teflon sheet and a kite string, and a waterdispersible adhesive composition after being immersed in ethyl acetateand dryed

The measurement results are shown in Table 5.

TABLE 5 Example Example Example Example Example Example Evaluation ofphysical properties 14 15 16 17 18 19 Example 20 Adhesive Adhesion PeelInitial 5.7 5.7 5.0 2.5 2.1 2.1 2.1 optical to glass rate at 60° C. for18.5 18.5 14.0 7.9 11.8 11.8 11.8 film (peel [300 mm/min.] 40 hoursadhesion [N/25 mm]) Adhesion and Heat A A A A A A A fixation resistance(90° C.) Moist heat A A A A A A A resistance (60° C./90% RH) Water Gelfraction (%) 95 95 91 85 86 86 86 dispersible adhesive composition Comp.Comp. Comp. Comp. Comp. Example Example Example Example Example ExampleExample Evaluation of physical properties 21 22 14 15 16 17 18 AdhesiveAdhesion Peel Initial 7.4 1.2 2.1 2.1 3.4 Water dispersible optical toglass rate at 60° C. for 24.9 10.3 6.0 6.0 6.8 adhesive film (peel [300mm/min.] 40 hours composition could adhesion not be obtained [N/25 mm])because cohesion Adhesion and Heat A A A C C occurred during fixationresistance the (90° C.) polymerization. Moist heat A A C B C resistance(60° C./90% RH) Water Gel fraction (%) 92 87 93 93 87 dispersibleadhesive composition

While the illustrative embodiments and examples of the present inventionare provided in the above description, such are for illustrative purposeonly and it is not to be construed restrictively. Modification andvariation of the present invention which will be obvious to thoseskilled in the art are to be covered in the following claims.

What is claimed is:
 1. An adhesive optical film comprising: an opticalfilm; an adhesive layer laminated on at least one surface of the opticalfilm; and an under coat layer containing an oxazoline group-containingpolymer, which is interposed between the optical film and the adhesivelayer.
 2. The adhesive optical film according to claim 1, wherein theunder coat layer is made of a mixture of an oxazoline group-containingpolymer and a polyamine-based polymer.
 3. The adhesive optical filmaccording to claim 1, wherein the under coat layer is made of a mixtureof an oxazoline group-containing polymer and a compound having aplurality of carboxyl groups.
 4. The adhesive optical film according toclaim 1, wherein the under coat layer is made of a mixture of anoxazoline group-containing polymer, a polyamine-based polymer and acompound having a plurality of carboxyl groups.
 5. The adhesive opticalfilm according to claim 1, wherein the oxazoline group-containingpolymer has a principal chain being an acryl skeleton, and has anoxazoline group in a side chain of the principal chain.
 6. The adhesiveoptical film according to claim 2, wherein the polyamine-based polymerhas a principal chain being an acryl skeleton, and has apolyethyleneimine chain in a side chain of the principal chain.
 7. Theadhesive optical film according to claim 3, wherein the compound havinga plurality of carboxyl groups has a number average molecular weight of1000 or more.
 8. The adhesive optical film according to claim 1, whereinthe under coat layer is made of a water dispersible polymer.
 9. Theadhesive optical film according to claim 1, wherein the adhesive layeris made of an acrylic adhesive.
 10. The adhesive optical film accordingto claim 9, wherein the acrylic adhesive is water dispersible.
 11. Theadhesive optical film according to claim 1, wherein the adhesive layerhas a functional group which reacts with an oxazoline group and/or anamino group.
 12. The adhesive optical film according to claim 11,wherein the functional group, which reacts with an oxazoline groupand/or an amino group, is a carboxyl group.